Vinnitsa National Pirogov Memorial Medical University Biological and General Chemistry Department Medical chemistry course

SYSTEMATIC COURSE Lecture material Module 1. Acid-base equilibrium and chemistry of complexes in biological liquids For practical lessons of medical chemistry for foreign students

Vinnitsa 2010

Systematic course is approved by academic council of National Pirogov Memorial Medical University,Vinnitsa (minutes 5 from 2.03.2011)

Authors: Assistant Professor Smirnova O.V. Assistant Professor Chervyak M.M. Assist. Shunkov V.S.

Reviewer:

Azarov O.S.- Candidate of chemistry science, assistant professor Department of Biological and General Chemistry VNMU

Marchak T.V.- Candidate of chemistry science, assistant professor Department of Physiological Agriculture and Live Stock Breeding and Chemistry VNAU

Shitova T.V. Senior lecturer Department of Russian and Ukrainian languages Head of English language courses VNMU

Printing group VNMU: Text editor Shunkov V.S. Computer editor Shunkov V.S. Secretary Koroleva N.D.

CONTENT 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. Periodic system of D.I. Mendeleev. Electron-atomic structure of elements and ions. Biogenic s-elements, chemical properties, biological role, application in medicine. Biogenic -elements, chemical properties, biological role, application in medicine. Biogenic d- elements, chemical properties, biological role, application in medicine. The formation of complexes in biological systems. Preparation of the solutions and calculation of its concentrations. The basic concepts of volumetric analysis. Neutralization method. Base Standardization. Neutralization method. Acid Standardization. Acid-base equilibrium in human body. pH of biological liquids. Buffer systems, classification and mechanism. Buffer capacity. The role of buffer solutions in biological systems. Colligative properties. Osmosis. 4 11 20 33 38 46 56 64 67 71 74 80

TOPIC 1: Periodic system of D.I. Mendeleev. Electron-atomic structure of elements and ions.
The periodic table of the chemical elements (also periodic table of the elements or just the periodic table) is a tabular display of the chemical elements. Although precursors to this table exist, its invention is generally credited to Russian chemist Dmitri Mendeleev in 1869, who intended the table to illustrate recurring ("periodic") trends in the properties of the elements. The layout of the table has been refined and extended over time, as new elements have been discovered, and new theoretical models have been developed to explain chemical behavior. The periodic table is now ubiquitous within the academic discipline of chemistry, providing a useful framework to classify, systematize, and compare all of the many different forms of chemical behavior. The table has found many applications in chemistry, physics, biology, and engineering, especially chemical engineering. The current standard table contains 118 elements to date Classification: Groups A group or family is a vertical column in the periodic table. Groups are considered the most important method of classifying the elements. In some groups, the elements have very similar properties and exhibit a clear trend in properties down the group. These groups tend to be given trivial (unsystematic) names, e.g., the alkali metals, alkaline earth metals, halogens, pnictogens, chalcogens, and noble gases. Some other groups in the periodic table display fewer similarities and/or vertical trends (for example Group 14), and these have no trivial names and are referred to simply by their group numbers. Periods A period is a horizontal row in the periodic table. Although groups are the most common way of classifying elements, there are some regions of the periodic table where the horizontal trends and similarities in properties are more significant than vertical group trends. This can be true in the dblock (or "transition metals"), and especially for the f-block, where the lanthanides and actinides form two substantial horizontal series of elements. Blocks Because of the importance of the outermost shell, the different regions of the periodic table are sometimes referred to as periodic table blocks, named according to the subshell in which the "last" electron resides. The s-block comprises the first two groups (alkali metals and alkaline earth metals) as well as hydrogen and helium. The p-block comprises the last six groups (groups 13 through 18) and contains, among others, all of the semimetals. The d-block comprises groups 3 through 12 and contains all of the transition metals. The f-block, usually offset below the rest of the periodic table, comprises the rare earth metals. The chemical elements are also grouped together in other ways. Some of these groupings are often illustrated on the periodic table, such as transition metals, poor metals, and metalloids. Other informal groupings exist, such as the platinum group and the noble metals. (Table 1.1)

Main-group elements s-block 1A 2A 3B 4 B

1 2 3 4 5 6 7

Transition elements d-block 5B 6B 7B 8B

3A 1B 2B

p-block 4A 5A 6A

8A 7A

f-block

4 5 s-elements p-elements d-elements f-elements Table 1.1

Russian chemistry professor Dmitri Ivanovich Mendeleev and Julius Lothar Meyer independently published their periodic tables in 1869 and 1870, respectively. They both constructed their tables in a similar manner: by listing the elements in a row or column in order of atomic weight and starting a new row or column when the characteristics of the elements began to repeat. The success of Mendeleev's table came from two decisions he made: The first was to leave gaps in the table when it seemed that the corresponding element had not yet been discovered. Mendeleev was not the first chemist to do so, but he went a step further by using the trends in his periodic table to predict the properties of those missing elements, such as gallium and germanium. The second decision was to occasionally ignore the order suggested by the atomic weights and switch adjacent elements, such as cobalt and nickel, to better classify them into chemical families. With the development of theories of atomic structure, it became apparent that Mendeleev had inadvertently listed the elements in order of increasing atomic number. Periodicity of chemical properties : The main value of the periodic table is the ability to predict the chemical properties of an element based on its location on the table. It should be noted that the properties vary differently when moving vertically along the columns of the table than when moving horizontally along the rows. Trends of groups Modern quantum mechanical theories of atomic structure explain group trends by proposing that elements within the same group have the same electron configurations in their valence shell, which is the most important factor in accounting for their similar properties. Elements in the same group also show patterns in their atomic radius, ionization energy, and electronegativity. From top to bottom in a group, the atomic radii of the elements increase. Since there are more filled energy levels, valence electrons are found farther from the nucleus. 5

From the top, each successive element has a lower ionization energy because it is easier to remove an electron since the atoms are less tightly bound. Similarly, a group will also see a top to bottom decrease in electronegativity due to an increasing distance between valence electrons and the nucleus. Trends of periods Elements in the same period show trends in atomic radius, ionization energy, electron affinity, and electronegativity. Moving left to right across a period, atomic radius usually decreases. This occurs because each successive element has an added proton and electron which causes the electron to be drawn closer to the nucleus. This decrease in atomic radius also causes the ionization energy to increase when moving from left to right across a period. The more tightly bound an element is, the more energy is required to remove an electron. Similarly, electronegativity will increase in the same manner as ionization energy because of the amount of pull that is exerted on the electrons by the nucleus. Electron affinity also shows a slight trend across a period. Metals (left side of a period) generally have a lower electron affinity than nonmetals (right side of a period) with the exception of the noble gases. Electronic structure of atoms and ions. To understand why pure substances have particular compositions and properties we need to know about the "electronic structure" of the atoms (i.e. the way the electrons are arranged about the nucleus of the atoms of different elements). Then we can rationalize the ratio in which atoms combine and whether they are molecular, polymeric or ionic, [e.g. why gaseous nitrogen consists of discrete N2 molecules; methane, ammonia, water and hydrogen fluoride consist of discrete molecules of CH4, NH3, H2O, HF respectively; why sodium chloride consists of Na+ and Cl ions; why metals exist in nature mainly as cations, Mx+; why free-radicals are reactive. Early last century a model of the atom (Bohr model) in which electrons circulated around the nucleus in orbits, just as planets do around the sun, was developed. This model proved inadequate to explain many phenomena and was replaced in the 1920's, when it waspostulated that the behaviour of electrons in atoms could be described by mathematicalequations similar to those used to describe the motion of standing waves in a string. Fromthis model the electrons can be visualised as electron clouds of various shapes with thenucleus of the atom at their centre. Electronic structure of atoms: The arrangement of electrons around the nucleus of the atom. The properties of atoms can be understood in terms of Quantum Theory, which involves the Heisenberg Uncertainty Principle and the Schrdinger Wave Equation. Quantum Theory: A theory that states that the energy of an object can only change by discrete steps. A change involves a packet of energy called a quantum. Heisenberg Uncertainty Principle: The position and momentum of a particle cannot both be known simultaneously. This implies that in an atom the position and momentum of an electron cannot both be known simultaneously. (Thus a model of an atom containing electrons in fixed orbits around the nucleus is untenable.) Schrdinger Wave Equation: A mathematical expression ascribing wave-like properties to matter. When applied to atoms it describes the properties of electrons in atoms. This equation gives rise to the concepts of energy levels, atomic orbitals and quantum numbers. Electronic energy levels: Allowed energies of electrons in atoms. Atomic orbital: A mathematical expression from the Schrdinger Wave Equation from which, for each energy level, the probability of finding the electron at different positions from the nucleus can be calculated. The atomic orbital can be depicted as an "electroncloud" with the nucleus at the centre, the denser the cloud the greater the probability of the electron being there. Only two electrons can occupy the same orbital. 6

Quantum numbers: Numbers which label the orbital and spin of an electron. Electron pair: Two electrons in the same orbital. They must have opposite spins. Spin of an electron: The intrinsic angular momentum of an electron. Occurs in only two senses denoted () and ()). Electron shells: The electrons in an atom exist in shells, each shell being made up of atomic orbitals or subshells. Principal quantum number: Symbol n, an integer, 1,2 3... which defines the shell. The smaller n is, the lower the energy of the electron (more energy required to remove the electron from the atom), and the closer on average it is to the nucleus. First character in designation of an orbital. Azimuthal quantum number: Symbol l, defines the subshell or kind of orbital, and can have the values 0,1,...,n-1. An orbital with l = 0 is called an s orbital; with l = 1 is called a p orbital; with l = 2 is called a d orbital; with l = 3 is called an f orbital. Second character in designation of an orbital. Magnetic quantum number: Symbol m1, specifies the particular orbital of a subshell and can have values -l, -l+1,...0,...,l-1,l. Spin quantum number: Symbol ms, specifies the spin of an electron and can have values of + () or - (). Occupancy of shells: The first shell, n = 1, can hold 2 electrons in one orbital, labelled 1s. (l = 0 for an s orbital) The second shell, n = 2, can hold 8 electrons in four orbitals, one labelled 2s and three labelled 2p. (l = 1 for a p orbital). The third shell can hold 18 electrons in nine orbitals, one 3s, three 3p and five 3d. (l = 2 for a dorbital) The fourth shell, n = 4, can hold 32 electrons in 16 orbitals, one 4s, three 4p, five 4d and seven4f. (l = 3 for an f orbital) Within a shell the energy levels of the orbitals (subshells) is s <p <d <f. The bottom line in each entry of the preceding periodic table gives the number of electrons in the shells in the ground state of that element [e.g. potassium, K, 2.8.8.1, has 2 in the first shell, 8 in the second, 8 in the third and one in the fourth.]. Ground state: The state of an atom when all the electrons are in the lowest allowed energy levels. Electron configuration: A statement of the arrangement of electrons in the orbitals [e.g. Cl, Each principal quantum number is shown only once and the number of electrons in each subshell is shown as a superscript following the symbol for the orbital. The ground state electron configuration of any element can be written down by filling the orbitals in order using the energy levels: 1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s <4f< 5d < 6p < 7s <5f [e.g. cobalt, Co, Z = 27, thus 27 electrons. 1s22s2p63s2p64s23d7. This may be written as 1s22s2p63s2p6d74s2.] (Table 1.2) 1s22s2p63s2p5]. Valence electrons: Those electrons in the outermost shell and in unfilled subshells [e.g. Cl has 7 valence electrons (3s2p5) and Co has 9 valence electrons (3d74s2)]. Valence electrons are involved in chemical bonds.

Quantum numbers n, l 6,2 5,3 7,0 6,1 5,2 4,3 6,0 5,1 4,2 5,0 4,1 3,2 4,0 3,1 3,0 2,1 2,0 1,0

Spectroscopic notation or subshell ( n, l ) 6d 5f 7s 6p 5d 4f 6s 5p 4d 5s 4p 3d 4s 3p 3s 2p 2s 1s

Maximum number Of electrons allowed In the subshell = 2 (2l + 1) 10 14 2 6 10 14 2 6 10 2 6 10 2 6 2 6 2 2

Table 1.2 Atomic number The atomic number of an element, Z, is equal to the number of protons that defines the element. For example, all carbon atoms contain 6 protons in their nucleus; so the atomic number "Z" of carbon is 6. Carbon atoms may have different numbers of neutrons; atoms of the same element having different numbers of neutrons are known as isotopes of the element. Atomic mass The mass number of an element, A, is the number of nucleons (protons and neutrons) in the atomic nucleus. Different isotopes of a given element are distinguished by their mass numbers, which are conventionally written as a super-index on the left hand side of the atomic symbol (e.g., 238U). In general, it differs slightly from the mass number as the mass of the protons and neutrons is not exactly 1 u, the electrons also contribute slightly to the atomic mass, and because of the nuclear binding energy. For example, the mass of 19F is 18.9984032 u. The only exception to the atomic mass of an isotope not being a natural number is 12C, which has a mass of exactly 12, because u is defined as 1/12th of the mass of a free carbon-12 atom. Basic Atomic Structure The number of protons in an atom or ion determines what element it is. (Table 1.3) For example, if a particle has 6 protons in it, it must be carbon.

(Subatomic Particles) Subatomic Particle Proton Electron Neutron

Mass ~ 1 a.m.u. ~ 0 a.m.u. ~ 1 a.m.u.

Charge +1 -1 0 Table 1.3

Basic Atomic Structure The atomic number of an atom or an ion is equal to its number of protons. Atomic Number = Number of Protons Example: If you look up potassium (K) in the periodic table, it has an atomic number of 19, meaning that all potassium atoms and all potassium ions contain 19 protons. Atomic Mass Number = (# of Protons) + (# of Neutrons) Example: A particle with 6 protons and an atomic mass number of 14 has 8 neutrons. A particles name will sometimes include the atomic mass number of the particle. For example, chlorine-37 is a chlorine atom that has an atomic mass number of 37, meaning that it has a total of 37 protons and neutrons in its nucleus. Since the atomic number for chlorine is 17, any chlorine atom or ion always has 17 protons. Therefore, a chlorine-37 atom has 20 neutrons, because 37 minus 17 equals 20. Ions = Charged Particles Ions are formed when atoms gain or lose electrons. Positive ions (cations) are formed when a neutral atom loses electrons. Negative ions (anions) are formed when a neutral atom gains electrons. Metallic atoms tend to lose electrons to form positive ions (also known as cations). Nonmetallic atoms tend to gain electrons to form negative ions (a.k.a. anions). Charge = (# of Protons) - (# of Electrons) Example: A particle with 34 protons and 36 electrons has a charge of -2. Isotopes Main articles: Isotope and Stable isotope Isotopes are atoms of the same element that have a different number of neutrons. Therefore, isotopes have the following characteristics: Isotopes have the same atomic number (same number of protons), but a different atomic mass number (a different number of neutrons). (Picture 1) Isotopes behave the same chemically, because they are the same element. The only difference is that one is heavier than the other, because of the additional neutrons. For example, carbon-12 and carbon-14 are both isotopes of carbon. Carbon-12 has 6 neutrons; carbon-14 has 8 neutrons. The atomic weight of an element (as it appears in the periodic table) is the weighted average of the atomic mass numbers of all of the isotopes for that element. For example, the atomic weight of carbon (as shown on the periodic table) is 12.011 a.m.u. (atomic mass units). However, there is no one carbon atom that has a mass of 12.011 a.m.u. Carbon exists as four different isotopes: carbon-11, carbon-12, carbon-13, and carbon-14, which have approximate atomic mass numbers of 11, 12, 13, and 14 a.m.u., respectively.

Picture 1.

10

TOPIC 2: Biogenic s-elements, chemical properties, biological role and application in medicine.
The s-block of the periodic table of elements consists of the first two groups: the alkali metals and alkaline earth metals, plus hydrogen and helium. These elements are distinguished by the property that in the atomic ground state, the highestenergy electron is in an s-orbital. Except in hydrogen and helium, these electrons are very easily lost to form positive ions. The helium configuration chemically exceeds stablility and thus helium has no known stable compounds; thus it is generally grouped with the noble gases. The other elements of the s-block are all extremely powerful reducing agents, so much that they never occur naturally in the free state. The metallic forms of these elements can only be extracted by electrolysis of a molten salt, since water is much more easily reduced to hydrogen than the ions of these metals. Sir Humphry Davy, in 1807 and 1808, was the first to isolate all of these metals except lithium, beryllium, rubidium and caesium. Beryllium was isolated independently by F. All the s-block metals are dangerous fire hazards which require special extinguishers to extinguish. Except for beryllium and magnesium, storage must be under either argon or an inert liquid hydrocarbon. They react vigorously with water to liberate hydrogen, except for magnesium, which reacts slowly, and beryllium, which reacts only when amalgamated with mercury to destroy the oxide film. Lithium has similar properties to magnesium due to the diagonal relationship with magnesium in the periodic table. The six elements belonging to group 1 of the periodic table, namely lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr) are called alkali metals. They constitute alkali metals because they readily dissolve in water to form hydroxides, which are strongly alkaline in nature. They also form alkaline oxides. The francium element is radioactive. Occurrence Lithium occurs mainly as silicate minerals such as spodumene [LiAl(SiO3)2], lepidolite [(Li,Na,K)2Al2,(SiO3)3 (F,OH)2] etc. It is the 35th most abundant element by weight. Compounds of sodium and potassium have been known from ancient times. Sodium and potassium are the seventh and eighth most abundant elements by weight in the Earth's crust and together make up over 4% of the Earth's crust by weight. NaCl and KCl also occur in large amounts in seawater. Rock salt (NaCl) is the major source of sodium. Potassium occurs mainly as deposits of KCl (sylvite), which is a mixture of KCl and NaCl (sylvinite) and double salt KCl MgCl2 6H2O (carnallite). Rubidium and cesium are obtained as a by-product of lithium processing. Francium being radioactive does not occur appreciably in nature. Nature of the compounds The compounds of the alkali metals are ionic in nature. Alkali metals form cations readily by losing the valence electrons (due to the low ionization energies and large atomic sizes). They go on to form ionic bonds with the non-metals of the 'p' block. Sodium carbonate In anhydrous form, sodium carbonate is described by the chemical formula Na2CO3. In crystalline state sodium carbonate exists as Na2CO3 10H2O (decahydrate) and is called washing soda. It is a white crystalline solid, which loses water (effloresces) to dry air to yield monohydrate. Na2CO3+ 10 H2O Na2CO3H2O + 9H2O Sodium carbonate is used; 1.As a filler in the detergent industry, 2.For washing purposes, 3.For softening hard water, 4.In the manufacture of many useful compounds such as, sodium hydroxide, borax (Na2B4O7), hypo (Na2S2O3) etc. 5.In the paper and paint industry. 11

Sodium bicarbonate is also known as baking soda. It's formula is NaHCO3. On heating, it decomposes to give sodium carbonate and CO2 is liberated. 2NaHCO3 Na2CO3 + H2O + CO2 Sodium bicarbonate is used for preparing baking powder and as a general treatment for acidity and mild indigestion i.e. as an effervescent drink (ENO salt). The electronic configurations of alkali metals Z 1 3 11 19 37 55 87 Element Hydrogen Lithium Sodium Potassium Rubidium Caesium Francium Nom. of electrons 1 2, 1 2, 8, 1 2, 8, 8, 1 2, 8, 18, 8, 1 2, 8, 18, 18, 8, 1 2, 8, 18, 32, 18, 8, 1 Table 2.1 Ionization energies Alkali metals have the lowest ionization energy in each period. Within the group, as we go down, the ionization energies of alkali metals decrease due to their atomic size being the largest in their respective periods. In large atoms the valence electrons are loosely held by the nucleus and are easily lost, leading them to have low ionization energies and acquiring stable noble gas configurations. On moving down the group, the atomic size increases and the number of inner shells also increases, increasing the magnitude of screening effect and consequently, the ionization energy decreases down the group. The second ionizations energies of alkali metals are very high. The removal of an electron from alkali metals causes the formation of monovalent cations having very stable electronic configurations (same as that of noble gases). Therefore, it becomes very difficult to remove the second electron from the stable noble gas configurations, giving very high second ionization energy values (IE2). (Table 2.2) Table 2.2 I ElectroII metallic Eo value (V) 3.03 -2.71 - 2.92 The itive of an element is expressed in terms of the tendency of its atom to release electrons: Physical property Ionization Energy KJ mol-1 Li 520 7298 Na 496 4562 K Rb 419 403 3051 2633 -2.9 -2.93 3 Cs 376 2230

positive or character electroposcharacter

M M+ + e All the alkali metals are strongly electropositive or metallic in character, since they have low ionization energies and their atoms readily lose the valence electron. As the ionization energies decrease down the family, the electron releasing tendency or electropositive character is expected to increase down the family. Oxidation states All alkali metals have only one electron in their valence shell. They exhibit an oxidation state of +1 in their compounds and can lose the single valence electron readily to acquire the stable configuration of a noble gas. Thus, they form monovalent ions, M+ (e.g., Li+, Na+, K+, Rb+, Cs+). Since the second ionization energies are very high, they cannot form divalent ions. Thus, alkali metals are univalent and form ionic compounds. Characteristic flame coloration 12

As the alkali metals have very low ionization energies, the energy from the flame of a bunsen burner is sufficient to excite the electrons of alkali metals to higher energy levels. The excited state being unstable, these electrons return to their original energy levels, emitting extra energy, which gives characteristic flame colorations. The different colors of the alkali metals can be explained on the basis of amount of energy absorbed for excitation of the valence electron. Physical property Flame colour Li crimson red Na Yellow K pale violet Rb violet Cs bluish Table 2.3

Francium 1 Table 2.4 Alkali metals are in the same group of the Periodic Table, and thus they also show a regular gradation in physical properties like boiling and melting points. Thus Alkali metals are a group of metals that have almost same physical and chemical properties: Table: Properties of Alkali metals Alkali Metals Combined state (in compounds) Shiny, white, solid metals. Can be cut with a Physical state knife. Valence eletrons One valence electron in each alkali metal. Electrical Conduction Good conductors Electropositive; metallic nature increase down Nature the group. Reactivity Highly reactive Liberate Hydrogen on reacting with water and Reaction with water/acids acids; react vigorously and explosively. Types of compounds formed Electrovalent (Ionic) compounds Atomic size Increases down the group. Lowest ionization energy (because they lose Ionization energy electrons). Reducing/Oxidizing agents Strong reducing agents. Table 2.5 Physical Characteristics of Alkali Metals - the alkali metals are very reactive elements and not found in free state in nature. Hence alkali metals are normally stored in kerosene oil. Alkali metals are only isolated by electrolysis of their molten salts.The main physical characterestics of alkali metals are as: - all alkali metal are soft metals with low density. - the colour of most alkali metals are silvery white, but Caesium is a golden colour metal. - alkali metal's boiling and melting point decreases while we move in alkali group from top to bottom (Li have highest melting and boiling point). - alkali metals have low first ionization energy compared to all other group elements so due to this all alkali metals shows its specific flame color like Sodium flame color is yellow. - all alkali metals are very good conductors of heat and electricity. Property Occurrence

Properties of Alkali Metals: Table: Valence electron number of Alkali Metals Hydrogen Lithium Sodium Potassium 1 1 1 1

Rubidium 1

Cesium 1

Chemical Characteristics of Alkali Metals 13

All alkali metals are the most electropositive and least electronegative elements, they react with all types of nonmetals. Alkali metals are strong reducing agents. The value of standard electrode potentials of all alkali metals are negative, which indicates its strong tendency to form cations like (Li+, Na+ , K+ , Rb+, Cs+ and Fr+) in solution. The main chemical properties of alkali metals are given below. All alkali reacts with oxygen to form their coresponding oxide. Like when Li reacts with O2 then Li2O forms. 4Na + O2 2Na2O Few alkali metals also form peroxides and superoxides. 2K2O + O2 2K2O2 Aklali metals reacts with halogen to form alkali halides (eg: NaCl, KBr, LiF, CsI etc.). 2Na + I2 2NaI Alkali metals react with water very rapidally, When an Alkali metal reacts with water (H2O) then their corresponding alkali hydroxide form. Li2O + H2O 2LiOH Alkali metals are ionic compounds (except LiF, it is covalant compound because its cation size is small). Action with Hydrogen Formation of hydrides All alkali metals react with hydrogen to form hydrides that are ionic in nature (M+H-). 2M + H2 2M+H(M = Li, Na, K, Rb, or Cs) - reactivity of alkali metals with hydrogen increases from Li to Cs. - ionic character of the hydrides increases from Li to Cs. The decrease in ionization energy down the group permits easy availability of electrons to hydrogen, forming H- ion. - stability of hydrides decreases from Li to Cs because the M-H bond becomes weak as the size of the alkali metal increases from Li to Cs. This causes the stability of hydrides to decrease. - the hydrides behave as strong reducing agents and their reducing nature increases down the group. Action of Halogens Formation of halides Alkali metals combine readily with halogens to form ionic halides M+X-. For example, 2M + X2 2MX (X = halogen)

2Na + Cl2 2NaCl -reactivity of alkali metals with halogen increases down the group because of corresponding increase in electropositive character (decrease in ionization energy). -all metal halides are ionic crystals. Lithium iodide is slightly covalent as it has the smallest cation, which exerts maximum polarizing power and iodide ion being the largest anion can be polarized to the largest extent. -all alkali metal halides are soluble in water except LiF, as it has a high lattice energy combined with a small cation and anion, making it insoluble in water. Properties of Alkali Metals and Halogens Alkali metals: alkali metals have less density compared to other metals. 14

they have loosely bound valence electrons. they contain large radii in the periods they have low ionization energy and electronegativity. they are highly reactive in nature. Action with Air Formation of oxides All the alkali metals on exposure to air or oxygen burn vigorously, forming oxides on the surface of the metals. Lithium forms monoxide (Li2O), sodium forms the peroxide (Na2O2) and the other elements form superoxides. (MO2: M = K, Rb, Cs). 4Li + O2 2Na + O2 Li2O Na2O2 (monoxide) (peroxide)

M + O2 MO2 (0superoxide) (M = K, Rb, Cs) The alkali metal oxides are basic in nature because they dissolve in water to form alkali metal hydroxides. Na2O(s) + 2H2O(l) Peroxides give hydrogen peroxide also 2NaOH(aq)

Na2O2(s) + 2H2O(l) 2NaOH(aq) + H2O2(aq) Action Towards Water Formation of hydroxides Hydroxides and hydrogen gas result from the reaction of alkali metals with water. 2Na + 2H2O 2K + 2H2O 2NaOH + H2(g) 2KOH + H2

Hydration of ions The alkali metal ions are highly hydrated. The smaller the size of the ion, the greater is the degree of hydration. Thus, Li+ ion gets much more hydrated than Na+ ion which in turn is more hydrated than K+ ion and so on. The extent of hydration decreases down the group. As a result of larger hydration of Li+ ion than Na+ ion, the effective size of Li+ ion is more than that of Na+ ion. Further the ionic radii in water (called hydrated ionic radii) decreases in the order: Li+> Na+> K+> Rb+ > Cs+ (Table 2.6) Rb+ Cs+ 152 167 228 226 67.5 68.0 Table 2.6 As a result, the hydrated Li+ ion being largest ionic size, has the lowest mobility in water. On the other hand, the hydrated Cs+ ion being smallest in size has the highest mobility in water. Uses of Alkali Metals: Lithium metal is used to make useful alloys, for example with lead to make white metal bearings for motor engines, with aluminium to make aircraft parts, and with magnesium to make armour plates. It is used in thermonuclear reactions. Lithium is also used to make electrochemical cells. Sodium is used to make a Na/Pb alloy needed to make PbEt4 and PbMe4. These organolead 15 Ion Ionic radius (pm) Hydrated radius (pm) Ionic mobility (ohm-1 cm2 mol-1) Li+ 76 340 33.5 Na+ 102 276 43.5 K+ 138 232 64.5

compounds were earlier used as anti-knock additives to petrol, but nowadays vehicles use lead-free petrol. Liquid sodium metal is used as a coolant in fast breeder nuclear reactors. Potassium has avital role in biological systems. Potassium chloride is used as a fertilizer. Potassium hydroxide is used in the manufacture of softsoap. It is also used as an excellent absorbent of carbon dioxide.Caesium is used in devising photoelectric cells. Uses of Group 1 Elements: Alkali Metals and Compounds: 1) Sodium chloride is used as common salt. 2) Sodium is used in the preparation of Borax. 3) Potassium bromide is used in photography. 4) Potassium is used in the manufacture of NPK fertilizers. 5) Potassium hydroxide and sodium hydroxide is used in the manufacture of detergents. 6) Potassium chlorate is used in production of explosives. 7) Rubidium and Francium are radioactive and are used in chemical researches. 8) Sodium and Potassium are the vital nutrients in the human body. They help in Na- K pump. 9) Sodium- bicarbonate is used in baking and is also known as baking powder 10) Sodium compounds are also used as preservatives Ex:- MSG(monosodium glutamate). Introduction to alkali earth metals properties: The elements of 2nd A group of the periodic table are called the alkaline Earth metals. These are called alkaline earth metals because the oxides of these bases are alkali and they are found in the earth crust. Below are the following alkaline earth metals; Be (4), Mg (12), Ca (20), Sr (38), Ba (56), Ra (88) Electronic Configuration: These elements have two electrons in the s -orbital of the valence shell. Their general electronic configuration may be represented as [noble gas] ns2. Like alkali metals, the compounds of these elements are also predominantly ionic. (Table 2.7) Element Beryllium Magnesium Calcium Strontium Barium Radium Symbol Be Mg Ca Sr Ba Ra Electronic configuration: 1s22s2 1s22s22p63s2 1s22s22p63s23p64s2 2 1s 2s22p63s23p63d104s24p65s2 1s22s22p63s23p63d104s24p64d105s25p66s2 [Rn]7s2 Table 2.7

Atomic and Ionic Radii: The atomic and ionic radii of the alkaline earth metals are smaller than those of the corresponding alkali metals in the same periods. This is due to the increased nuclear charge in these elements. Within the group, the atomic and ionic radii increase with increase in atomic number. Ionization Enthalpies: The alkaline earth metals have low ionization enthalpies due to fairly large size of the atoms. Since the atomic size increases down the group, their ionization enthalpy decreases. The first ionization enthalpies of the alkaline earth metals are higher than those of the corresponding Group 1 metals. This is due to their small size as compared to the corresponding alkali metals. It is interesting to note that the second ionization enthalpies of the alkaline earth metals are smaller than those of the corresponding alkali metals. Physical Properties: The alkaline earth metals in general are silvery white, lustrous and relatively soft but harder than the alkali metals. Beryllium and magnesium appear to be somewhat grayish. The melting and boiling points of these metals are higher than the corresponding alkali metals due to their smaller 16

sizes. The trend is, however, not systematic. Because of the low ionization enthalpies, they are strongly electropositive in nature. The electropositive character increases down the group from Be to Ba. Calcium, strontium and barium impart characteristic brick red, crimson and apple green colours respectively to the flame

Chemical Properties of Alkaline earth metals: The alkaline earth metals are less reactive than the alkali metals. The reactivity of these elements increases on going down the group. 1) Reactivity towards air and water: Mg + 2H2O 2) Reactivity towards the halogens: M + X2 MX2 Mg(OH)2 + H2

(X = F, Cl, Br, l)

3) Reactivity towards hydrogen: All the elements except beryllium combine with hydrogen upon heating to form their hydrides, MH2. BeH2, however, can be prepared by the reaction of BeCl2 with LiAlH4. 4) Reactivity towards acids: The alkaline earth metals readily react with acids liberating dihydrogen. M + 2HCl MCl2 + H2

Uses of Bleacing Powder It is used; 1) as a disinfectant and germicide especially in the sterilization of drinking water. 2) for manufacture of chloroform. 3) for making wool unshrinkable. 4) as an oxidising agent in industry. 5) mainly as bleaching agent for cotton, linen and wood pulp. However, delicate articles like straw, silk, ivory, etc., are not bleached by bleaching powder. Carbonic acid is a dibasic acid that gives rise to two series of salts, carbonates (normal salts) and bicarbonates (acid salts), due to successive removal of the replaceable hydrogens from H2CO3. H2CO3 NaHCO3 + H2O

NaHCO3 + NaOH Na2CO3 + H2O Bicarbonates of calcium and magnesium are responsible for temporary hardness of water. Preparation By passing carbon dioxide through an alkali With excess of carbon dioxide, the carbonate first formed changes to bicarbonate With NaOH 2NaOH + CO2 Na2CO3 + H2O + CO2 With Ca(OH)2 17 Na2CO3 + H2O
sodium carbonate

2NaHCO3
sodium bicarbonate

Ca(OH)2 + CO2 CaCO3 + H2O + CO2

CaCO3 + H2O Ca(HCO3)2

By precipitation Heavy metal carbonates are precipitated from their salt solutions with washing soda. BaCl2 + Na2CO3 BaCO3 + 2NaCl Bicarbonates of only alkali metals exist in solid state, even though carbonates of many metals are known. Bleaching powder is also called calcium chlorohypochlorite because it is considered as a mixed salt of hydrochloric acid and hypochlorous acid. It is represented as:

Preparation It is manufactured by the action of chlorine on dry slaked lime, Ca(OH)2 at 40oC. Ca(OH)2 + Cl2 Ca(OCl)Cl + H2O This is the Odling view about its formation. There is another view proposed by Clifford according to which bleaching powder is a mixture of calcium hypochlorite and basic calcium chloride. 2Ca(OH)2 + 2Cl2 CaCl2 + Ca(OH)2 + H2O 2Cl2 + 3Ca(OH)2 Ca(OCl)2 + CaCl2 + H2O CaCl2Ca(OH)2H2O Ca(OCl)2 + CaCl2Ca(OH)2H2O + H2O

The manufacture of bleaching powder is carried out in Backmann's plant as follows: It consists of a vertical cast-iron tower. The tower is provided with a hopper at the top, two inlets near the base (one for chlorine and other for hot air) and an exit for waste gases near the top. The tower is fitted with eight shelves at different heights each equipped with rotating rakes. The slaked lime is introduced through the hopper and it comes in contact with chlorine, which slowly moves upwards. Bleaching powder is collected in a barrel at the base. The chlorine used in the manufacture of bleaching powder should be dilute and the temperature should be maintained below 40oC. Biological Importance of Sodium and Potassium Sodium cation (Na+) is an important cation of extracellular fluids of animals including human beings which is known to mediate some enzymes in the animal body as well as in plants Sodium ions are relatively harmless except when present in large quantities of amounts in which case they might cause hypertension in the environment. The saline water containing excessive amounts of sodium chloride is harmful or injurious to plants and aquatic life because of the toxicity of Na+ ions. The potassium ion is essential to all organisms with the possible exception of blue green algae. It is a major cation of intracellular fluid of animal cells. It is moderately toxic to mammals but only when injected intravenously. It acts as a catalytic enzyme. Sodium pump/ Na+ - K+ pump 18

The sodium (Na+) and potassium (K+) ions, taken together, constitute what is known as Na+ pump or simply as sodium pump. The sodium pump mechanism plays an important role in the salinity tolerance in plants. Calculating sodium and potassium ions in plants is an important factor in salt tolerance. The function of this pump is genuinely a biological process which goes on occurring in each and every cell of all animals. Although the discussion of the exact mechanism of the functioning of this pump is beyond the scope of the review yet it may be adequate to stay that it transfers Na+ ions from the intracellular fluids to the extracellular fluids with the aid of proteins known as carrier proteins. Simultaneously it transfers potassium K+ ions from the extracellular fluids to the intracellular fluids. Since each operation of the pump (i.e. each cycle of this biological process) pumps out larger number of sodium ions from the cell than the quantity of K+ ions that it pumps into the cell, the interior of the cell acquires an excess negative (-ve) charge and the exterior of the cell acquires an excess positive charge (+ve). K+ This results in the development of electrical potential gradient across the cell membrane which is responsible for the transmission of nerve signals in animals. The Na+ -K+ pump also accommodates the volume of the cell. Without the being of the Na+-K+ pump in the cell, the cell would have swelled in volume and finally brusted. Picture 1. The biological role of S elements

19

Element

Location and role in the body

Herbal drugs H2O2 3%antiseptic; a local haemostatic; HCl 8,2-8,3% with reduced gastric acidity. NaCl 0,9% saline (isotonic solution) a simple blood substitution; for the preparation of medicinal substances; NaCl 4-10% hypertonic solution; NaHCO3 baking soda, antacid; Na2SO4lenitive; CaCl2 antiallergic, antiinflammatory drug, increases blood clotting. Cagluconate anti-inflammatory effect; 2CaSO42H2O burnt plaster casts; MgSO4 25%solution, a strong purgative; MgO magnesia, the antacid effect; MgCO3Mg(OH)23H2O white magnesia, the antacid effect; 3MgO4SiO2H2O talcum powder, adsorbing agent for powders;

Toxic effect, antidotes -

Element organogen

Na

Extracellular cation. Buffer systems, smosis, K, Na - pump

Ca

Bone and dental tissue in the form of compounds:a5(OH)(PO4)3or CaCO3 3Ca3(PO4)2H2O

Mg

Intracellular ion; action against the spasm

Ba

Retina

Soluble saltsBa2+ are toxic; Ba(SO4)2 contrast agent in Xantidotes ray Na2SO4, MgSO4 Table 2.8

20

TOPIC 3: Biogenic -elements, chemical properties, biological role, application in medicine.

The elements belonging to groups 3 to 8 of the periodic table are the p-block elements. Elements of these groups have configuration ns2np16 (except He). The absence of dorbitals in second period and presence of d or f in heavier elements have significant effects on their properties. Apart fromthis the presence of all the three types of elements metals, metalloids and nonmetals bring diversification in the chemistry of these groups. The p-block includes all the noble gases except helium, allthe nonmetals except hydrogen, all the metalloids, and even a few metals, including Al, Sn, and Pb.Three of the p-block elements - O, Si, and Al - are the mostabundant elements in Earths crust. Six p-block elements - C, N, O, P, S, and Cl - are among theelements making up the bulk of living matter.Five others - B, F, Si, Se, and I - are required in traceamounts by most plant and animal life.C and S can occur in the free state. p - the elements are called chemical elements, which is filsl p-sublevel outer energy level. These are the elements III-A, IV-A, V-A, VI-A and VII-A groups of the periodic system of D.I.Mendeleev. Electronic configuration, i.e. distribution of electrons in energy levels and sublevels, for atoms and ions of p - elements can be illustrated by P and Br: P 1s22s22p63s23p3 P-3 1s22s22p63s23p 0

Br 1s22s22p63s23p63d104s24p5 Br-1 1s22s22p63s23p63d104s24p6. Some of these families from these group you can find here!

The nitrogen family

The element nitrogen (N), phosphorus (P), arsenic (As),antimony (Sb) and bismuth (Bi) constitute group 15 of theperiodic table.The first two elements of this group, nitrogen andphosphorus are non-metals, the next two, arsenic antimonyare metalloids whereas the last element, bismuth, is a metal.All the elements of this group have five electrons in theirvalence shells.Their general valence shell electronic configuration isns2np3. Physical properties Melting points and boiling points. These increase on going down the group. However, the melting point of bismuth is usually low. This may presumably be due to more tendency of Bi toform three rather than five covalent bonds (inert paireffect). Thus, there are weak forces of attraction between theiratoms in solid state, accounting for its low m.pt. Atomic radii. Atomic radii, as expected, increases with increase inatomic number. Ionization energy and electropositive character. The first ionisation energy decreases regularly down thegroup due to increase in the size of atoms andscreening effect of intervening electrons.The ionisation energies of this group are much higherthan those of corresponding elements of group 14.This is due to the increase in nuclear charge and extrastable configurations of the elements of this group.The extra stability of configurations is attributed to the exactly half-filled p-orbitals in their valence shells.Due to high ionisation energies, the elements of this group are less electropositive than elements of group 14.Electropositive (or metallic) character increases on going down the group due to decrease in ionisation energies.The fact is reflected by the change in metallic characterfrom nitrogen to bismuth. Oxidation States. All the elements of this group have five electrons in their valence shell.These elements require three more electrons to acquire noble gas configuration. However, though gaining of three electrons 21

requires alarge amount of energy yet it takes place only withnitrogen as it is the smallest and the most electronegative element of this group.N3 ion exists in the compounds such as Mg3N2, Ca3N2, etc.The other elements of the group form covalent compounds in which their formal oxidation state is 3.For example, calcium phosphide (Ca3P2), sodium arsenide (Na3As), zinc antimonide (Zn3Sb2) and magnesium bismuthide (Mg3Bi2).In addition to 3 oxidation state, the elements of this group also exhibit + 3 and + 5 oxidation states. Chemical properties Hydrides The elements of group 15 form hydrides having the general formula MH3. All these are covalent in nature. 1) The thermal stability of the hydrides decreases in the order: NH3> PH3> AsH3> SbH3> BiH3 It is because the strength of MH bond decreases down the group due to increase in the size of central atom. 2) These hydrides act as reducing agents.The least stable hydride (BiH3) acts as the strongest reducing agent whereas the most stable hydride (NH3) acts as a weakest reducing agent. 3) The boiling points of these hydrides vary as follows:
Hydride Boiling point (K) NH3 238.5 PH3 185.5 AsH3 210 SbH3 254 BiH3 290

NH3 molecules are associated by intermolecular Hbonds.As a result its boiling point is exceptionally high.The interparticle forces in PH3 are van der Waal forces due to which its boiling point is low.In moving from PH3 to BiH3 boiling points increase.This is due to the increase in the magnitude of van der Waal forces due to increase in molecular size. 4) Due to presence of a lone pair of electrons on the central atom in these hydrides, these act as good Lewis bases.The basic character decreases down the group.It is because of small size of nitrogen. The lone pair of electrons are concentrated on a small region so density per unit volume is more. Halides All the elements of group 15 form two series of halides, i.e., trihalides and pentahalides of the type MX3 and MX5.These trihalides are mainly covalent with the exception of BiF3 which is ionic.The ionic character of trihalides increases in going down the group.These trihalides except NX3 can be easily hydrolysed by water.The inability of trihalides of N to hydrolyse is attributed to the non-availability of vacant d-orbitals in nitrogen. The trihalides of P, As, Sb (especially fluorides and chlorides) act as Lewis acids and combine with Lewis bases). Except nitrogen other elements of this group form pentahalides. Nitrogen cannot form pentahalides because it cannot expand its covalency due to non-availability of d-orbitals in the valence shell.All the pentahalides act as Lewis acids.It is because the central atom can easily accept the halide ions (due to presence of vacant d-orbital) and can extend their co-ordination number. Oxides The elements of this group combine with oxygen directly or indirectly to form a large number of different types of oxides. All those elements form 2 types of oxides E2O3 and E2O5.All the oxides of nitrogen (except NO and N2O) and phosphorus are strongly acidic.Oxides of arsenic are weakly acidic; oxides of antimony are amphoteric and those of bismuth are weakly basic.As far as the stability of the oxides is concerned, it is found that oxides having elements in the higher oxidation state become less stable as we move down the group.This is because of the inert pair effect. Nitrogen Nitrogen is found in greater abundance in the atmosphere than anywhere else.There are only two important mineral sources of nitrogen: KNO3 and NaNO3.Nitrogen compounds occur in all living matter.Nitrogen molecule, N2, has a very strong N N triple bond. Consequently it is quite 22

unreactive and is used as an inert blanketing atmosphere in industrial operations.Liquid nitrogen is used in low-temperature applications.The only important commercial method of producing nitrogen is the fractional distillation of liquid air. Preparation of dinitrogen In laboratory, dinitrogen is prepared by heating aqueous solution of ammonium chloride with sodium nitrite. NH4Cl(aq) + NaNO2 N2(g) +2H2O(l) + NaCl(aq) Small amount of NO and HNO3 are also formed in this reaction; these impurities can be removed by passing the gas through aqueous sulphuric acid containing some potassium dichromate. Properties of dinitroge Some of the physical properties of dinitrogen are: 1) It is colourless, tasteless and odourless gas: 2) It is non-toxic. 3) It has very low solubility in water (23.2 xm3per litre of water at 273 K and 1 atm.) 4) Its m.p. and b.p. are 63.2 K and 77 K respectively. Chemical properties Dinitrogen has a very little chemical reactivity at ordinary temperatures.It is neither combustible nor supporter of combustion.It may be noted that nitrogen is neither strongly electronegative to act as good oxidising agent nor strongly electropositive to act as good reducing agent. Reaction with highly electropositive metals like lithium, calcium, magnesium, etc. 6Li + N2 3Ca + N2 Reaction with non-metals like dihydrogen and dioxygen N2 + 3H2 N2 + O2 2NH3
Ammonia

2Li3N Ca3N2

2NO
Nitricoxide

Use of dinitrogen The main use of dinitrogen is in the manufacture ofammonia and other industrial nitrogen chemicals like calcium cyanamide.It also finds use where the presence of an inert gas is required. Liquid nitrogen is used as refrigerant to preserve biological materials, in freezing food articles and in cryosurgery. It is also used in gas filled mercury thermometers employed for measuring high temperatures. Ammonia (NH3) Preparation of ammonia By heating ammonium salts. (NH4)SO4
Amm.sulphate

2NH3 + H2SO4 NH3 + NaPO2 + H2O

Sod. metaphosphite

NH4NaHPO4
Amm. sodium hydrogenphosphate

23

When the ammonium salts of non-volatile acids such as ammonium sulphate, ammonium sodium hydrogen phosphate or ammonium phosphate are heated, ammonia is produced. By heating ammonium salts with a strong bases NH4Cl + KOH (NH4)2SO4 + 2NaOH KCl +H2O +NH3 Na2SO4 + 2H2O + 2NH3

Large scale preparation Ammonia is generally manufactured by Habers process which involves the direct combination of nitrogen and hydrogen. N2(g) + 3H(g) 2NH3(g); = 93.6kJ/mol . Chemical properties Basic Nature Aqueous solution of ammonia is basic in nature and turns red litmus blue. Its basic character is due to the formation of OH ions in aqueous solution. In gaseous state also, it reacts with acids to form salts NH3(g) + HCl(g) 2NH3(g) + H2SO4(l) NH4Cl(s) (NH4)2SO4

Complex Formation Ammonia acts as a Lewis base due to the presence of a lone pair of electrons on nitrogen and hence, forms a number of complexes with metal ions.Due to the tendency of complex formation the white precipitate of silver chloride dissolves in aqueous solution of ammonium hydroxide. Precipitation of heavy metal ions from the aqueous solutions of their salts Heavy metal ions like Fe3+, Al3+, Cr3+, etc., are precipitated from their aqueous salt solutions. FeCl3 +3NH4OH AlCl3 + 3NH4OH Fe(OH)3+ 3NH4Cl Al(OH)3 + 3NH4Cl

Use of ammonia Ammonia is used mostly to produce various nitrogeneous fertilizers (ammonium nitrate, urea, ammonium phosphate and ammonium sulphate). Liquid ammonia is also used as a refrigerant. Nitrogen forms a number of oxides in different oxidation states Details are given in the table 3.1 Oxidation Common methods of Name Formula state of preparation nitrogen Dinitrogen oxide [Nitrogen(I) oxide] Nitrogen monoxide [Nitrogen(II) oxide] Dinitrogen trioxide [Nitrogen(IV) oxide] N2O +1 NH4NO3 N2O + 2H2O 2NaNO2 + 2FeSO4 + 3H2SO4 Fe2(SO4)3 + 2NaHSO4 + 2H2O + 2NO 2NO + N2O4 2N2O3 24

Physical appearance and chemical nature colourless gas, neutral colourless gas, neutral blue solid, acidic

NO

+2

N2O3

+3

Nitrogen dioxide [Nitrogen(IV) oxide] Dinitrogen tetroxide [Nitrogen(IV) oxide] Dinitrogen pentoxide [Nitrogen(V) oxide]

2Pb(NO3)2 NO2 +4 2PbO2 N2O4 +4 2NO2 N2O4 4HNO3 + P4O10 4HPO3 + 2N2O5 colourless solid/liquid, acidic colourless solid, acidic 4NO2 + brown gas, acidic

N2O5

+5

Table 3.1 Nitric acid (HNO3) Manufacture (Ostwalds process). This method was established by Wilhelm Ostwald (1902). In this method, HNO3 is manufactured by oxidation of ammonia.It takes place in following steps. 1) Catalytic oxidation of ammonia A gaseous mixture containing pure and dry ammonia and dust free dry air in the ratio of 1:10 by volume is passed through a steel shell or aluminium converter having platinum gauze heated electrically to about 1100 K. Ammonia is oxidized to nitric oxide and the reaction is exothermic. 4NH3 + 5O2 4NO +6H2O

2) Oxidation of nitric oxide The nitric oxide obtained above is cooled and passed through a spacious chamber called oxidising chamber. The nitric oxide is oxidized to nitrogen dioxide. 2NO + O2 2NO2

3) Absorption tower The gases are then introduced in absorption tower which is packed with acid proof stones.Water sprayed from the top dissolves nitrogen dioxide in the presence of oxygen to give about 60% nitric acid. 3NO2 + H2O 2HNO3 + NO The acid flows down and is withdrawn from the tower with the help of a tap. Further concentration of nitric acid can be done to 98% acid by dehydration with concentrated sulphuric acid. Laboratory preparation In the laboratory, nitric acid can be prepared by heating NaNO3 or KNO3 with concentrated sulphuric acid in a glass retort and condensing the vapours of HNO3. NaNO3 + H2SO4 NaHSO4 + HNO3

Physical properties of nitric acid When pure, it is a colourless liquid.The impure acid is generally yellow due to the presence of nitrogen dioxide as impurity.Nitric acid containing dissolved nitrogen dioxide is known asfuming nitric acid.It has corrosive action on skin and produces painful blisters.Pure acid has a specific gravity of 1.54. It boils at 359 K and freezes to a white solid (m.p. 231 K). Chemical properties Acidic nature. 25

Nitric acid is one of the strongest acids. In aqueous solutions it gets almost completely ionised to form H3O+ ions and NO3ions. HNO3(aq) + H2O(l) H3O+(aq) + NO3-(aq) Therefore, nitric acid gives the usual reactions of acids.It turns blue litmus acid.It reacts with bases to form salts and water. For example: NaOH(aq) + HNO3(aq) It decomposes carbonates to give carbon dioxide. NaNO3(aq) + H2O(l)

Action on Metals When nitric acid reacts with metals, different products are formed depending upon the concentration of the acid and activity of the metal. Dilute nitric acid Magnesium and manganese are the only metals which liberate hydrogen from very dilute nitric acid ( 2%). Mg(s) + 2HNO2(aq) Mg(NO3)2 (aq) + H2 (g)

Mn(s) + 2HNO2(aq) Mn(NO3)2 (aq) + H2 (g) More active metals such as zinc, tin and iron, react with cold dilute nitric acid to form ammonium nitrate. 4Zn(s) + 10HNO3(aq) 4Zn(NO3)2(aq) + NH4NO3(aq) + 3H2O(l)

4Sn(s) + 10HNO3(aq) 4Sn(NO3)2(aq) + NH4NO3(aq) + 3H2O(l) However, with hot dilute nitric acid the ammonium nitrate, so formed gets decomposed resulting in the production of N2O. 4Zn(s) + 10HNO3(aq) 4Zn(NO3)2(aq) + N2O(g) + 5H2O(l) Less active metals like lead, silver, mercury and copper, react with dilute nitric acid to liberate nitric oxide NO as: 3Pb(s) + 8HNO3 (aq) 3Cu(s) + 8HNO3 (aq) 3Pb(NO3)2(aq) + 2NO(g) + 4H2O(l) 3Cu(NO3)2(aq) + 2NO(g) + 4H2O(l)

Concentrated nitric acid Metals such as lead, silver, copper and zinc, form nitrogen dioxide as: P4 + 20HNO3 4H3PO4 + 20NO2 + 4H2O

Pb(s) + 4HNO3(aq) Pb(NO3)2(aq) + 2NO2(g) + 2H2O(l) Metals, such as iron, aluminium and nickel are rendered passive by concentrated nitric acid. The passivity of these metals is attributed to the formation of thin protective layer of metal oxide on the surface of metal which cuts off the further action. Noble metals like gold and platinum do not react with nitric acid.However they dissolve in aqua regia (mixture of one part of conc. HNO3 and 3 parts of conc. HCl) forming respective chlorides. Phosphorus

26

Phosphorus is the eleventh most abundant element in Earths crust occurs exclusively in nature as phosphate: PO43 . Elemental forms: (I) White phosphorus, P4, can be cut with a knife, melts at 44.1 oC, is a non-conductor of electricity, and ignites spontaneously in air (it is stored under water). (II) Red phosphorus can be obtained by heating white phosphorus to about 300 oC in the absence of air. This allotrope of phosphorus forms long chains of phosphorus atoms joined together. Phosphine It is prepared by the following methods. From phosphides. By the reaction of phosphides with water. Ca3P2 + 6H2O
Calcium phosphide

2PH3 + 3Ca(OH)2
Phosphine

Na3P + 3H2O
Sodium phosphide

PH3 + 3NaOH

Laboratory method. Phosphine is prepared in the laboratory by heating white phosphorus with concentrated sodium hydroxide solution in an inert atmosphere of carbon dioxide or oil gas in a round-bottom flask. P4 + 3NaOH + 3H2O 3NaH2PO2 + PH3
Sod. hydrophosphite

Phosphine evolved is spontaneously inflammable due to the presence of phosphorus dihydride (P2H4, the liquid hydride) as impurity. Properties It is a colourless, poisonous gas with rotten fish smell. It is slightly soluble in water and its solution in water decomposes in presence of light giving red phosphorus and H2. On being absorbed in copper sulphate or mercuric chloride solution, corresponding phosphides are obtained. 3CuSO4 + 2PH3 Cu3P2 + 3H2SO4

3HgCl2 + 2PH3 Hg3P2 + 6HCl Like NH3 it is weakly basic and gives phosphonium compounds with acids. PH3 + HI PH4I

Phosphorus forms a number of oxo acids Details are given in the table 3.2 Hypo Ortho Name phosphorous phosphorous acid acid (phosphinic) (phosphonic) H3PO2 H3PO3 Formula Oxidation state of P +1 +3 Preparation of acid White P4 + alkali (Power reducing agent) P2O3 +H2O (weak reducing agent)

Ortho phosphoric acid H3PO4 +5

Pyro phosphoric acid

H4P2O7 +5 Heat phosphoric P4O10+ H2O acid (No reducing (No reducing properties) properties) Table 3.2

The Oxygen Family

27

Group 16 of periodic table contains five elements namely, oxygen (O), sulphur (S), selenium (Se), tellurium (Te) and polonium (Po). Group 16 of periodic table contains five elements namely, oxygen (O), sulphur (S), selenium (Se), tellurium (Te) and polonium (Po). These are collectively known as chalcogens or ore forming elements because many metal ores occur as oxides and sulphides. Oxygen, the most abundant elements, is an important constituent of atmosphere and ocean. It constitutes 46.6% of earths crust. Oxygen Oxygen is one of the most active non-metals and one of the most important. The chief reactions of elemental, atmospheric oxygen are oxidation processes. Uses of oxygen include: manufacture of iron, other metals, welding, manufacture of chemicals, water treatment, oxidizer, and respiration therapy. Ozone, O3, is a powerful oxidizing agent, especially in acidic solution. It is also found in the upper atmosphere. Sulphur Sulfur forms many compounds similar to those of oxygen.However They are differ in important way: hydrogen bonding in O compounds, but not in S compounds and S can employ an expanded valence shell, but O cannot. Elemental sulfur exists as several molecular species: solid - S8 , vapor - S2. Elemental sulphur is mined using the Frasch process. A small amount of sulphur is used directly in vulcanizing rubber and as a pesticide.

28

Physical properties Density As expected, the density increases down the group with the increase in atomic number. Melting and Boiling Points The melting and boiling points show a regular increase down the group.It is because as we move down the group the molecular size increases. As a result, the magnitude of van der Waal forces increase and hence the melting and boiling points also increase. Ionization energy These elements possess large values of ionization energies which decrease gradually from O to Po. Oxygen has very high ionization energy (1314 kJ mol1). The decrease in ionization energy from oxygen to polonium is due to increase in size of the atoms and increase in screening effect of the electrons belonging to lower shells. Metallic and non-metallic character Metallic character depends on ionization energy. Lesser the ionization energy greater will be the metallic character. As we move down the group, the ionization energy decreases and therefore the metallic character increase. Thus, the first four elements namely oxygen, sulphur, selenium and tellurium are non-metals. The non-metallic character is maximum in O and decreases down the group.Polonium, the last member of the group, is metallic in nature. Oxidation states All the elements have ns2np4electronic configuration of outermost shell in their atoms. Thus, these tend to acquire the noble gas configuration by sharing or gaining electrons. Oxygen, the first member of the family exhibits the oxidation state of 2 in its compounds owing to its high electronegativity.In addition to the oxidation state of 2, oxygen also exhibits an oxidation state of 1 in H2O2, zero in O2 and + 2 in OF2. Electronegativity Oxygen is strongly electronegative in character. The value of electronegativity decreases with increase in atomic number down the group. The value of electronegativity decreases with increase in atomic number down the group. Chemical properties Hydride These elements form volatile hydrides of H2E type such as H2O, H2S, H2Se, H2Te and H2Po. The volatile nature of hydrides first increases from H2O to H2S and then decreases. The low volatile character of water is due to the association of water molecules through hydrogen bonding. The decrease in volatile nature from H2S onwards is due to increased interactions among molecules due to increase in molecular size. These hydrides are weak lyacidic in nature. The acidic nature increased from H2O to H2Te. H2S is a weak diprotic acid. The increase in strength as acid on moving down the group is due to increase in size of the atoms. The distance between central atom and hydrogen increases as we move from O to Te which favours the release of hydrogen as proton.This order of acidity, however, cannot be explained in terms electronegativity of these elements. All the hydrides, except water, are reducing agents. The reducing character increase on moving from H2S to H2Te. This is presumably due to the increase in the size of the central atom due to which the strength of MH bond and also the stability decreas es down the group. Halide The elements of group 16 form a number of halides. The more important halides being hexa, tetra- and dihalides. The stability of halides is in the following order F> Cl< Br > I. The hexaflurorides of S, Se and Te i.e., SF6, SeF6, TeF6 have the central atom in sp3d2hybridised 29

state.These fluorides have octahedral structure.It is the small size of fluorine which brings out the maximum covalency. Hexahalides with Cl, Br and I are not formed. Due to the bigger size of these halogen atoms a coordination number of six is not achieved. Amongst the tetrafluorides of S, Se and Te, SF4 is gaseous SeF4 is liquid and TeF4 is solid. In tetrahalides sp3d hybridisation occurs and thus these have got a trigonal bipyramidal structure with one of the equatorial position occupied by a lone pair of election. Oxides The elements of this group form a number of oxides.All elements (except Se) form monoxide. All elements form dioxide with formula MO2.SO2 is a gas, SeO2 is a volatile solid while TeO2 and PoO2 are non-volatile crystalline solids. The acidic character of the dioxides decreases as we move down the group.All the group 16 elements form the trioxides, MO3. The best known trioxide is SO3. Oxygen Preparation of Dioxygen From oxygen rich salts Certain oxygen rich salts such as chlorates, permanganates, peroxides and nitrates on heatingdecompose to give dioxygen gas. 2KClO3(s)
Potassium chlorate

2KCl(s) + 3O2(g) Mn3O4 + O2

3MnO2
Manganese dioxide

Manufacture of Dioxygen From air The most economical method for commercial preparation of dioxygen involves liquefaction of air followed by fractional distillation of the liquid air thus obtained. From water Dioxygen can also be prepared by the electrolysis of water containing a small amount of a mineral acid or an alkali. 2H2O(l) 2H2(g) + O2(g)

Properties of Dioxygen 1) Dioxygen is colourless, tasteless and odourless gas. 2) It is slightly soluble in water. 3) Its solubility being approximately 30 cm3 per liter of water at 298 K. 4) Its slight solubility in water is responsible for sustaining the life of aquatic animals and also for the degradation oforganic wastes in water bodies. 5) It is appreciably soluble in alkaline pyrogallol solution. 6) Liquid oxygen exhibits, paramagnetism, i.e., it is slightly attracted by magnet. Chemical reactions Action with litmus. It is neutral to litmus. Reaction with metals. Active metals like Na, Ca, etc. react at room temperature forming the respective oxides. 4Na(s) + O2(g) 2Na2O2(s)
Sodiumperoxide

30

2Ca(s) + O2 (g) 2CaO(s) Metals like Mg burn in dioxygen to form magnesium oxide. 2Mg(s) + O2(g) 2MgO(s) Metals like iron and aluminium combine with dioxygen on heating to form their respective oxides. 4Fe(s) + 3O2(g) Reaction with non-metals. Phosphorous P4(s) + 5O2 Dinitrogen N2(g) + O2(g) Reaction with compounds. Hydrogen chlorid 4HCl(g) + O2(g) Sulphur dioxide 2SO2(g) + O2(g) 2SO3(g) 2H2O(l) + 2Cl2(g) 2NO(g) P4O10(s) 2Fe2O3(s)

Sulphur dioxide (SO2) Sulphur dioxide is formed by burning sulphur in air or roasting metal sulphides in the presence of air. S8 + 8O2 4FeS2 + 11O2 8SO2 2Fe2O3 + 8SO2

Sulphuric acid (H2SO4) It is the most important oxyacid of sulphur and is known from ancient times.It is called oil of vitriol because in early days it has been prepared from ferrous sulphate crystals (green vitriol) and has an oily appearance. Because of its large applications in industries it is also known as the king of chemicals. Manufacture of sulphuric acid Sulphuric acid is manufactured by contact process. The process involves the following steps: Production of sulphur dioxide. It is carried out by burning powdered sulphur or roasting of sulphur rich ores. S8 + 8O2 4FeS2 + 11O2 Conversion of SO3 into H2SO4. SO3 is absorbed in conc. H2SO4 to get oleum. SO3 + H2SO4 31 H2S2O7 8SO2 2FeO3 + 8SO2

Oleum may then be diluted with calculated quantity of water to get H2SO4 of required concentration. H2S2O7 + H2O 2H2SO4

The Halogens
Halogens are all non-metals with valence shell electron configuration. Halogen elements exist as diatomic molecules, X2. Fluorine is the most reactive, iodine is the least. The oxidizing power decreases from F2 to I2. Halogens occur naturally only as the halides (X) and are converted to halogens usually by electrolysis. Physical properties Melting and Boiling Points. Melting and boiling points increase with increase in atomic number. The heat of fusion as well as heat of vapourisation also increase with the increase in atomic number. This indicates that the strength of intermolecular forces of attraction between the molecules increases with the increase in atomic number. Atomic and Ionic Radii Atomic and ionic radii are small and increase regularly down the group form fluorine to iodine because new electronic shells are added. Ionization Energies Ionization energies of all the halogens are very high. Therefore, they have a less tendency to lose electron. However, this tendency increases down the group because the distance of valence shell from nucleus increases. Iodine is capable of forming stable compounds in which it exists as I- ion. Colour Halogens are coloured. The colour of different halogens are as follows: Details are given in the table 3.3 Halogen Fluorine Chlorine Colour Pale Yellow Greenish Yellow ns2np5

Bromine Reddish brown

Iodine Dark violet Table 3.3

Chemical properties All the halogens are very reactive but amongst them fluorine is the most reactive.As we move down the group, reactivity decreases. This is due to the decrease in electronegativity and increase in bond dissociation energy. In general, a halogen of low atomic number oxidizes halide ions of higher atomic number i.e., F2 displaces Cl2, Br2 and I2 from their salts, Cl2 displaces Br2 and I2 where as Br2 displaces iodine from its salts, e.g., F2 + XCl2 + 2X2F- + X2 2Cl- + X2 (X = Cl, Br, I) (X = Br, I)

Oxidising power The halogens act as strong oxidising agents. It is because of their high electron affinities that they have great tendency to take up electrons. The oxidising power of the halogens decreases ongoing down the group from fluorine to astatine. Hydride Halogens combine with hydrogen to form volatile halides of the formula HX. Except HF, all other hydrides HCl, HBr and HI are gases. HF is a liquid because of intermolecular hydrogen bonding. HF.HF.HF. 32

Location and role Toxic effect, Element Herbal drugs inhalides the body antidotes All the hydrogen act as acids in their aqueous solutions. The acidic strength varies in the H 3BO3 disinfectant properties (eye order. Carbohydrate-phosphorus B and ear drops); metabolism HF < HCl < 2HBr HI antiseptic Na B4O7< (bur) Al(OH)3 absorbent and antacid Halides properties; The halogens, in general, react with almost all the metals and non-metals except, He, Ne and Ar almagel - water to form a wide variety of binary halides. With metals like Na, suspension; K, Mg, etc. having low ionisation Alwhich kaolin, energies, the halogens react to form ionic halides have got boiling and melting points. 2O32SiO 22H 2Ohigh blood, nerve cells in the brain; adsorbing action; As the electronegativity of the halogens decreases down the group the ionic character decreases in Al involved in the construction of the Al2(SO4)3 hemostatic, the order. epithelial and connective tissue antimicrobial and MF > M Cl > MBraction > M I for water purification. Oxides KAl(SO4)212H2O (lum) Halogens do not combine with oxygen directly but their oxides with oxygen can be prepared hemostatic, antimicrobial action; indirectly. For example, oxygen difluoride, OF is prepared by the action of on 2% sodium 2 (arbol, activated charcoal) fluorine hydroxide solution. The compounds of oxygen with fluorine are called fluorides because fluorine flatulence adsorb gases,as toxic Coal dust is more electronegative than oxygen. Most of these compounds are endothermic and unstable and substances; anthracosis; are likely to explode resulting in the formation of stable products. more O2 stimulatory effect on CO2 carbon C rganogen, 21,15% respiratory centers, inhalations, monoxide; The biological role of P elements baths; antidote - xygen Table 3.4 NaHCO3 baking soda, antacid. SiO2dust causes Lens of the eye, hair; gives Silicon carbide and oxide used in Si strength, elastic fabric. dentistry. silicosis. 2+ (CH3COO)(OH)Pb lead water, Pb toxic, binds The biological role has not been Pb SH-groups of anti-inflammatory, antimicrobial studied proteins, enzymes; action. NH4OH 9,5-10,5% solution, irritating effect on the CNS; rganogen; 3,1%; proteins, NH4Cl diuretic; N nucleic acids. NaNO2 vasodilator; N2O inhaled anesthetics. rganogen; 0,95% nucleic acids, ATP,bone and dental tissue in the Calcium glycerophosphate a means honky poison; form of antidote 0,5% P of fortifying; compounds:a5(OH)(PO4)3or solution uSO4 ATP the energy product. CaCO3 3Ca3(PO4)2H2O As2O3 white As rganic compounds for the treatment of sexually transmitted arsenic, a powerful Brain tissue, muscle, involved in diseases; poison antidotes As the synthesis of hemoglobin. As2O3 necrotising tissue (used in Na2S, MgS, dentistry) Na2S2O3 O2 + CO2 stimulates the O rganogen; 62,4%; respiratory center; S (leaned) antimicrobial action ; SO2 disinfectant ; Na2SO4 weakpurgative; SO2 irritating to rganogen; 0,16%; proteins, S rganic compounds - sulfa drugs mucous membranes S amino acids - cysteine, antimicrobialaction ; of the respiratory methionine; H3C-SO-CH3 dimixed; well tract and eyes. penetrates through biological membranes, anti-inflammatory effect. Excess fluoride Bone and dental tissue Ca5(PO4)3F F NaF, KF, sedatives causes fluorosis or speckled enamel 33 Cl Gastric juice, extracellular anion HCl 8,2-8,3% at low acidity of Cl2 gas, irritating

TOPIC 4: Biogenic d- elements, chemical properties, biological role, application in medicine.

The elements which have partially filled d-orbitals either ground state or in one or more of their ions, are called d-block elements or outer transition elements. Their properties are intermediate between s-block elements and p-block elements. They are more electropositive than p-block elements but less electropositive than s-block elements. They form ionic compounds in their lower oxidation state and covalent compounds in higher oxidation states. They are all metals and have electronic configuration ns2, (n-1)d1 to 10 General characteristics of d-block elements Electronic configuration of first series of d-block elements. (Table 4.1) For first series (Sc z = 21) to (Zn z = 30) Sc Ti V Cr Mn Fe Co Ni Cu Zn (z = 21) (z = 22) (z = 23) (z = 24) (z = 25) (z = 26) (z = 27) (z = 28) (z = 29) (z = 30) 1s2 1s2 1s2 1s2 1s2 1s2 1s2 1s2 1s2 1s2 2s2 2s2 2s2 2s2 2s2 2s2 2s2 2s2 2s2 2s2 2p6 2p6 2p6 2p6 2p6 2p6 2p6 2p6 2p6 2p6 3s2 3s2 3s2 3s2 3s2 3s2 3s2 3s2 3s2 3s2 3p6 3p6 3p6 3p6 3p6 3p6 3p6 3p6 3p6 3p6 4s2 4s2 4s2 4s1 4s2 4s2 4s2 4s2 4s1 4s2 3d1 3d2 3d3 3d5 3d5 3d6 3d7 3d8 3d1
0

3d1
0

Table 4.1 Metallic character All transition elements are metals. Atomic size The atomic size of d-block elements decreases from Sc to Zn due to increase in nuclear charge. Their atomic sizes are smaller than that of s-block elements. Ionization potential The I.P. values of transition elements are intermediate between those of s-block and p-block elements. This shows that they are more electropositive than p-block elements and less reactive than s-block elements. Due to intermediate values I.P. they form ionic compounds as well as covalent compounds. Melting and boiling point Melting and boiling point of these elements are very high (except Zn). These higher values are due to small atomic radii of transition elements which provides greater inter atomic forces of attraction. They are very hard . Conductivity Transition elements are good conductor of heat and electricity. Colour Except zinc all the transition metals complex ions are colourless due to presence of unpaired electrons. The colour of ions can be explained on the basis of "Crystal field theory". According to this theory ,the bonding between ligands and a metal ion is electrostatic. The ligands surrounding the metal ion and create an electrostatic field around its d-orbitals. This field split '5' degenerated dorbitals in to two sets of different energies. 34

a) A high energy pair (eg) of dx2-dy2 and dz2. b) A low energy trio (t2g) of dxy, dyz, dzx. In many cases difference of energy between two sets 'eg' and 't2g' is equivalent to a wavelength in the visible region. Thus absorbing visible light, an electron may be able to move from lower energy set t2g to higher energy set eg. In doing so, some of the component wavelength of white light is removed, so the remaining component wavelength of light reflected or transmitted shows the colour. For example: Cu+2 (blue), V+3 (green), Co+2 (pink), Fe+2 (green), Fe+3 (yellow), Ti+3 (purple). At different oxidation states, same element produce different colours. General Features The d-block elements is the collective name for groups 3 to 12 in the periodic table. They are so called because a d-subshell is being filled. Here only the first row, from scandium to zinc, will be considered. Appearance Most of the d-block elements are considered to be metals, with a common lustrous metallic appearance. All but copper and gold have a silvery colour. General Reactivity These elements have d electrons in their valence shells, and this gives them different characteristics to other metals in the periodic table. They each exist in several oxidation states except scandium and zinc; many of their compounds are coloured; and they readily form complexes by acting as Lewis acids. Occurrence and Extraction The first six elements, scandium to iron, occur mainly as the oxides in various mineral deposits. The most abundant of these is iron, found chiefly in magnetite and haematite, both commonly known as iron ore. The remainder of the elements occur mainly as sulfides such as zinc blende. Each element is extracted from the appropriate mineral by various extraction methods. The extraction of iron, however, is of immense importance as steel - basically a mixture of iron and carbon - is used in greater quantities world-wide than any other metal. Steel is produced from iron ore in two main stages: (1) a blast furnace produces impure iron from iron ore (2) the impure iron is then purified and alloyed with other metals to produce steel. Physical Properties All these elements are hard, rigid and have good thermal and electrical conductivities. They have high melting and boiling points. Chemical Properties The chemistry of the d-block elements is governed by the fact that most exhibit several oxidation numbers. This is because the energies of all the d electrons are very similar. The d electrons also confer properties on these elements not found elsewhere: - they easily form complexes - their complexes are often coloured - some complexes are paramagnetic - they make good catalysts. The chemical properties of these elements and their many complexes is extensive, and not suitable for further study here. Oxidation States

35

As stated earlier, most of the d-block elements exist in several oxidation states - for example, the oxidation number of iron can be 0, +2, +3 and +6. The widest range of oxidation numbers is for manganese, which has a lowest oxidation number of 0 and a highest oxidation number of +7. There are general tendencies concerning the oxidation numbers: (a) the 1st and last elements, scandium and zinc, have only 1 oxidation number. (b) all the elements except zinc can have oxidation number +3 (c) all the elements except scandium can have oxidation number +2 (d) from scandium to manganese, the highest oxidation number = the number of 4s electrons + the number of 3d electrons (e) from manganese to zinc, low oxidation numbers are common. Industrial Information The d-block elements are used in many thousands of applications. Iron is the most widely used element because it is converted to steel, which consists of iron with 0.2 - 1.7% carbon. The addition of carbon hardens the iron and gives it better resistance to corrosion. Special steels can be prepared by the addition of small quantities of other elements stainless steel contains 18% chromium and 8% nickel. Iron and steel are extensively used in our society. Other important uses of some of these elements include titanium in aircraft and spaceship manufacture. Titanium is less dense than other d-block elements, and this lightness, coupled with its extra hardness, make it more suitable than aluminium in high-flying aircraft and space vessels. Chromium is often used for electroplating, and alloyed with nickel to make nichrome - used in electrical components as its electrical resistance hardly varies with temperature. Copper is used as protective sheeting as it is more resistant to oxidation than other elements. The green patina that forms on exposure to air is copper(II) carbonate, sulfate or chloride. Copper is also used in electrical cables. Zinc is used in protecting steel by galvanising, and in alloys, eg brass (copper and zinc). Variable oxidation state The multiple oxidation states of the d-block (transition metal) elements are due to the proximity of the 4s and 3d sub shells (in terms of energy). All transition metals exhibit a 2+ oxidation state (both electrons being lost from the 4s and all have other oxidation states (common). (Table 4.1) Zn Sc Ti V Cr Mn Fe Co Ni Cu +2 +3 +4 +2 +3 +4 +5 +2 +3 +4 +6 +2 +3 +4 +6 +7 +2 +3 +6 Table 4.2 Coordinated ligands Ligands are the molecules (or ions) which donate an electron pair to form a dative covalent bond with the central transition metal atom (forming a complex molecule or ion). Coordination Complexes These are species which are formed around a central atom, with other atoms, ions or molecules donating an electron pair to form a covalent bond to this central atom. The result is a "complex" usually an ion but may also be a molecule. (Table 4.2) Complex Shape Ligands Coordination number Name +2 +3 +2 +3 +1 +2 +2

+3

36

[Fe(H2O)6]3+ [Fe(CN)6]3[CuCl4]3[Cu(NH3)4]2+ [Ag(NH3)2]+ Ni(CO)4

octahedral octahedral tetrahedral square planar linear tetrahedral

Water cyanide CNchloride ClAmmonia Ammonia carbon monoxide

6 6 4 4 2 4

hexa-aqua iron III ion hexacyano ferrate III ion tetrachloro cuprate I ion tetra-ammine copper II ion diammine silver I ion tetracarbonyl nickel 0 molecule

Table 4.3 Coloured compounds The color in the transition metals (d-block) is predominantly due to the splitting of the d shell orbitals into slightly different energy levels. As a result, certain wavelengths of energy can be absorbed by the d-block elements (with electrons jumping between these slightly different energy levels), resulting in the complement color being visible. Colour is affected by both the oxidation state of the transition metal and the type of ligand (Table 4.3) Complex ion [Fe(H2O)6]3+ [Fe(H2O)6]2+ [Cu(H2O)6]2+ [Cu(NH3)4]2+ [CuCl4]2 Oxidation state of metal III II II II II Colour pale green yellow blue deep blue green Ligand Water Water Water ammonia chloride ion Table 4.4 Crystal field theory Magnetism Transition metals and their ions often have unpaired 'd' electrons which produce an asymmetric magnetic field that can be detected. This is called paramagnetism (Table 4.4) Examples: Complex ion [Fe(H2O)6]3+ [Cr(H2O)6]3+ [Cu(H2O)6]2+ [Ni(NH3)6]2+ [CoCl4]2Electronic configuration [Ar]4s0 3d5 [Ar]4s0 3d3 [Ar]4s0 3d9 [Ar]4s0 3d9 [Ar]4s0 3d7 37 No of unpaired electrons 5 3 1 2 3 Magnetism paramagnetic paramagnetic paramagnetic paramagnetic paramagnetic

Table 4.5 Catalytic activity 'd' block elements make good catalysts due to their multiple oxidation states (hence their ability to react with different species and produce a path of lower activation energy, and so allow the reaction to proceed at a faster rate). Another possible reason for their catalytic activity is their available 'd' orbitals which allow reacting molecules to co-ordinate to the surface of the transition metal which in turn weakens the bonding within the molecule allowing it to react. The biological role of D elements Element Location and role in the body Hemoglobin (Fe2+); catalase and peroxidase (Fe2+ Fe3+); cytochrome c (Fe2+ Fe3+) hematopoietic processes and electron transfer Enzymes pepsin, trypsin, exchange of glucose Lungs, muscles, an activator of enzymes Processes of hematopoiesis Pancreas; effect on carbohydrate metabolism Enzyme xanthine oxidase, purine metabolism Herbal drugs FeCl36H2O hemostatic; iron supplements to treat iron deficiency anemia Toxic effect, antidotes ompounds Cr+6 cause skin and mucous membranes arcinogen Excess disturbes purine metabolism endemic gout Excess of copper Wilsons disease; uSO4 an antidote for poisoning by white phosphorus -

Fe

Cr Mn Co Ni Mo

Chromium picolinate for diabetes KMnO4antiseptic Vitamin B12(cyanocobalamin) -

Cu

Liver; processes of hematopoiesis

Zn

The enzyme carbonic anhydrase, endocrine glands, the processes of reproduction.

Ag

Kidney, endocrine glands

ZnSO4 (0,1-0,25%) astringent, anti-inflammatory effects (eye drops); ZnO antibacterial astringent (in dermatology) AgNO3 (lapis) bactericidal, astringent, protargol, colloid silver colloidal silver) bactericidal action HgCl2 (sulema)) (1:1000) antiseptic; Hg2Cl2 ((calomel) laxative HgO(ointment) in dermatology Hg in thermometers

A pair of HgandHgCl2 affect the central nervous system; spilled mercury bind FeCl3, S, KMnO4 Table 4.6

Hg

Kidney

38

TOPIC 5 : The formation of complexes in biological systems.

1. Actuality of the topic: many chemical substances are identified in quantitive and qualitive analysis conversing to the complexes. The complexes have phisiological significance in the processes of breathing, photosynthesis, biological oxidation, and enzymatic catalysis. 2.General aim: to explain the physiological action of the complexes and their application as medicals. 3. Actual aims and abilities: to know the structure and nomenclature of complexes; to be able to write the instability constant of complexes. 4. Literature: 4.1. Lecture materials; 4.2. "Chemistry"3th ed. 2001. J. Mc Murry and R. Fay; Prentice Hall, Upper Saddle River, New Jersey 07458, ISBN 0-13-087205-9; 4.3. Ebbing, D.D. and S.D. Gammon. 2002. General Chemistry. Seventh Edition. Houghton Mifflin Co., Boston, MA. A complex system is a system whose properties are not fully explained by an understanding of its components. Complex systems consist of a large number of mutually interacting and interwoven parts, entities or agents. They are woven out of many parts, the Latin complexus comes from the Greek word pleko or plektos, meaning "to plait or twine." (Gell-Mann). Complex systems are also often used as a broad term addressing a research approach which includes ideas and techniques from chaos theory, artificial life, evolutionary computation and genetic algorithms. Complex ions Complexes are the charged species in which a metal atom is joined by coordinate covalent bond to neutralize a molecule and\or negative ion. For example: [Cu(NH3)4]SO4 [Cu(NH3)4]Cl2 [Al(H2O)6]Cl3 The structure of complex compounds can be explained with the coordinatory Verners theory.According to it: 1. Central atom or the complex-maker is the positive charged metal ion. 2. Ligands the electroneutral or negative charged ions that are attached to the central ion. They make the interior coordinatory sphere. 3. The exterior coodinatory sphere is made by ions (positive or negative charged) that are situated further from the central ion. 4. Coordination number shows the number of ligands.

39

Picture 1 The coordination number as usual is equal to the double valency or the charge of the central ion. The central ion charge 1+ 2+ 3+ 4+ Complex ion is the central ion + ligand To find the charge of the central ion we need to add charges of all ions in the neutral molecule of complex compound [Ni(NH3)6]SO4 Na3[AlF6] SO42thus (-2)+x=0 Na+ thus (+1)3+x=0 x=+2 x=-3 [Ni(NH3)6]2+ [AlF6]3Nomenclature of complexes 1. The cation is named first followed by the anion 2. If there is more than one ligand, we use prefixes bis- or tris- . The name of ligand is inclosed in parentheses. 3. In the formula of the complex compound the symbol of the central atom is written first, folowed by the formulas of neutral ligands and negatively charged ligands. 4. The formula of the complex ion is set off by brackets. 5. The names of anionic ligands are modified by substituting the suffix o- for the ususal ending. Thus we have Cl- chloro OH- hydroxo CO32- carbonato CN- cyano Coordination number 2 4 6 (may be 4) 8 (may be 6) Table 5.1

6.The names of neutral ligands are not changed. 7.Exceptions are H2O aquo NH3 ammine 8. The charge of the metal ion is indicated by a Roman numeral following the name of metal Ag(I), Cu(II), Co(II) 9. If the complex is anion, the suffix ate is added. Thus we have K4[Fe(CN)6] - potassium hexacyanoferrate(II) K2[CoCl4] potassium tetrachlorocobalt [Cu(NH3)4]SO4 - tetramminecopper(II)sulfate [Ni(NH3)6]SO4 hexamminenickel(II) sulfate Na3[AlF6] - sodium hexafluorinoaluminate 40

[Co(H2O)5]Cl3 pentaaquocobalt (III) chloride Na2[Zn(CN)4 - sodium tetracyanozincate(II) [Ni(NH3)6](OH)2 hexamminenickel(II)hydroxide [Ag(NH3)2]2SO4 bisamminesilver(I)sulfate The types of complex compounds I. According to the charge of the complex ion Cation complex [Ag(NH3)2]OH Anion complex Cu2Fe(CN)6] 3) hydroxo-complexes Na2Zn(OH)4] 4) acido-complexes Cu2Fe(CN)6] 5) chelates a) cyclic II. According to the ligand nature 1) amoniocates [Zn(NH3)4]SO4 2) hydro-complexes [Cr(H2O)6]Cl3

b) interior complexes

Picture 2 Chelates are part of important biologically active compounds such as hemoglobin, chlorophyll and B12 vitamin. c) complexions (metal cations in association with EDTA) d) some organic compounds products of amines and acids interaction Dissociation The primary dissociation of the complex ion and exterior sphere is easy [Ag(NH3)2]OH[Ag(NH3)2]++ClThe secondary dissociation of the complex ion is more hard [Ag(NH3)2]+Ag++2NH3 We also need to find the constant of instability for the complex compounds It reflects the equilibria between ions that appeared after dissociation of the complex and nondissociated complex ions The equation of the instability constant will look like Kd=[Ag]+2[NH3]-/[Ag(NH3)2]+ Where Kd represents the instability constant of the complex ion. Geomery of the complex compounds Coordination number = 2 Complex ions in which two ligands are coordinated to a central metal atom, are invariably linear. For example: (H3NAgNH3)+ (NCAgCN)Coordination number =4 For a complex in which the metal ion forms four bonds, two different geometries are possible: the square planar complex and the tetrahedral complex. The square complexes can exist in two different forms with quite different properties cys and trans isomers. (Picture 3)

41

cys-isomer 3-coordination, 4-coordination, 5-coordination,

trans-isomer Picture 3 6-coordination, 7-coordination, 8-coordination

Picture 4 Isomerism The arrangement of the ligands is fixed for a given complex, but in some cases it is mutable by a reaction that forms another stable isomer. There exist many kinds of isomerism in coordination complexes, just as in many other compounds. (Picture 4) Stereoisomerism Stereoisomerism occurs with the same bonds in different orientations relative to one another. Stereoisomerism can be further classified into: Cis-trans isomerism and facial-meridional isomerism Cis-trans isomerism occurs in octahedral and square planar complexes (but not tetrahedral). When two ligands are mutually adjacent they are said to be cis, when opposite each other, trans. When three identical ligands occupy one face of an octahedron, the isomer is said to be facial, or fac. In a fac isomer, any two identical ligands are adjacent or cis to each other. If these three ligands and the metal ion are in one plane, the isomer is said to be meridional, or mer. A mer isomer can be considered as a combination of a trans and a cis, since it contains both trans and cis pairs of identical ligands. (Picture 5)

cis-[CoCl2(NH3)4+

trans-[CoCl2(NH3)4+

fac-[CoCl3(NH3)3

mer-[CoCl3(NH3)3 Picture 5

Optical isomerism Optical isomerism occurs when the mirror image of a compound is not superimposable with the original compound. It is called so because such isomers are optically active, that is, they rotate the plane of polarized light. The symbol (lambda) is used as a prefix to describe the left-handed propeller twist formed by three bidentate ligands, as shown. Similarly, the symbol (delta) is used as a prefix for the right-handed propeller twist. (Picture 6)

-[Fe(ox)33

-[Fe(ox)33

-cis-[CoCl2(en)2+

-cis-[CoCl2(en)2+ Picture 6

42

Structural isomerism Structural isomerism occurs when the bonds are themselves different. Linkage isomerism is only one of several types of structural isomerism in coordination complexes (as well as other classes of chemical compounds). Linkage isomerism occurs with ambidentate ligands which can bind in more than one place. For example, NO2 is an ambidentate ligand: it can bind to a metal at either the N atom or at an O atom. Coordination number = 6 The six groups surrounding the metal ion in such complexes as Fe(CN)63+; Co(NH3)63+ are located at the corners of the regular octahedron. The metal ion is located at the center of the octahedron. (Picture 7)

Picture 7 Electronic structure of complex ions According to the valence-bond model electron pairs donated by the ligands hybrid orbitals associated with the central metal atom. For example in the ion [Zn(NH3)4]2+ The Zn2+ion doesnt have electrons at the fourth external level. 1s2 2s2 2p6 3s2 3p6 3d10 4s0 In the ammine molecule Nitrogen has the undivided electronic pair. The four electronic pairs(donation) areb located at the free orbitals of Zn2+ion (acception)

Picture 8 Meaning 1. In analytical chemistry they are used for qualitative analysis and tests for specific ions 4Fe Cl3+3K4[Fe(CN)6] Fe4[Fe(CN6)]3+12KCl Determination of the Fe3+ ions in the solution. 2. For metals dividing and getting extremely clear metals(Au, Ag) 3. As colorizing substances 4. Stimulators of the important biochemical processes ferments Naming complexes The basic procedure for naming a complex: When naming a complex ion, the ligands are named before the metal ion. 43

Write the names of the ligands in alphabetical order. (Numerical prefixes do not affect the order.) Multiple occurring monodentate ligands receive a prefix according to the number of occurrences: di-, tri-, tetra-, penta-, or hexa. Polydentate ligands (e.g., ethylenediamine, oxalate) receive bis-, tris-, tetrakis-, etc. Anions end in o. This replaces the final 'e' when the anion ends with '-ate', e.g. sulfate becomes sulfato. It replaces 'ide': cyanide becomes cyano. Neutral ligands are given their usual name, with some exceptions: NH3 becomes ammine; H2O becomes aqua or aquo; CO becomes carbonyl; NO becomes nitrosyl. Write the name of the central atom/ion. If the complex is an anion, the central atom's name will end in -ate, and its Latin name will be used if available (except for mercury). If the central atom's oxidation state needs to be specified (when it is one of several possible, or zero), write it as a Roman numeral (or 0) in parentheses. Name cation then anion as separate words (if applicable, as in last example) Examples: [NiCl42 tetrachloronickelate(II) ion [CuNH3Cl53 amminepentachlorocuprate(II) ion [Co(NH3)5Cl]SO4 pentaamminechlorocobalt(III) sulphate The coordination number of ligands attached to more than one metal (bridging ligands) is indicated by a subscript to the Greek symbol placed before the ligand name. Thus the dimer of aluminium trichloride is described by Al2Cl4(2-Cl)2. Structure of coordination complexes The ions or molecules surrounding the central atom are called ligands. Ligands are generally bound to the central atom by a coordinate covalent bond (donating electrons from a lone electron pair into an empty metal orbital), and are said to be coordinated to the atom. There are also organic ligands such as alkenes whose pi bonds can coordinate to empty metal orbitals. An example is ethene in the complex known as Zeise's salt, K+[PtCl3(C2H4)]-. Complexation in biological systems Complex called the compound at the sites of the lattice crystal which are difficult and complex ions which pass into solution as a result of dissociation. In 1983 swiss chemist Alfred Werner created a theory that explains the structure of complex compounds. The basis of coordination theory Werner: a) the central atom, or complexing agent - is a positively charged metal ion (less non-metal); b) ligands - are electrically neutral or negatively charged ions, which are located (coordinated) around the central atom. Central atom and ligands constitute the inner coordination sphere; c) the outer coordination sphere are positively or negatively charged ions, which are at a greater distance from the central ion and are not affiliated with it; d) the coordination number shows the number of ligands. As a rule, the coordination number is twice the valence of the metal. (Table 5.1) For example: Component parts Complexing Ligand Inner coordination sphere Outer coordination sphere Cationic complex [u(NH3)4]SO4 u2+ NH3 u(NH3)4 SO4-2 44 Anionic complex K2 [Pt(Cl)6] Pt+4 Cl Pt(Cl)6 K+

Coordination number Charge of the complex ion

4 [u(NH3)4]2+

6 [Pt(Cl)6] 2Table 5.2

The electronic configuration of the complexes gives them some important properties: Colour
Hydrated ion

OH- little OHexcess NH3 little NH3 excess CO32-

Fe(II) [Fe(H2O)6]2+ pale green soln [Fe(H2O)4(OH)2] dark green ppt [Fe(H2O)4(OH)2] dark green ppt [Fe(H2O)4(OH)2] dark green ppt [Fe(H2O)4(OH)2] dark green ppt FeCO3 dark green ppt

Fe(III) [Fe(H2O)6]3+ yellow/brown soln [Fe(H2O)3(OH)3] brown ppt [Fe(H2O)3(OH)3] brown ppt [Fe(H2O)3(OH)3] brown ppt [Fe(H2O)3(OH)3] brown ppt [Fe(H2O)3(OH)3] brown ppt + bubbles

Co(II) [Co(H2O)6]2+ pink soln [Co(H2O)4(OH)2] blue/green ppt [Co(H2O)4(OH)2] blue/green ppt [Co(H2O)4(OH)2] blue/green ppt [Co(NH3)6]2+ straw coloured soln CoCO3 blue/green ppt

Cu(II) [Cu(H2O)6]2+ blue soln [Cu(H2O)4(OH)2] blue ppt [Cu(H2O)4(OH)2] blue ppt [Cu(H2O)4(OH)2] blue ppt [Cu(NH3)4(H2O)2]2+ deep blue soln CuCO3 turquoise ppt

Al(III) [Al(H2O)6]3+ colourless soln [Al(H2O)3(OH)3] white ppt [Al(OH)4]colourless soln [Al(H2O)3(OH)3] white ppt [Al(H2O)3(OH)3] white ppt [Al(H2O)3(OH)3] white ppt + bubbles

Cr(III) [Cr(H2O)6]3+ green soln [Cr(H2O)3(OH)3] green ppt [Cr(OH)3]3green soln [Cr(H2O)3(OH)3] green ppt [Cr(NH3]6]3+ green soln [Cr(H2O)3(OH)3] green ppt + bubbles

Table 5.3 Most of the chemical elements contained in the organs and tissues have complex ompound with proteins and other biopolymers. This protein, amino acids, nucleic acids, peptides, fatty acids, carbohydrates, vitamins, hormones, enzymes. Complexing ability of bioligands can be explained by the presence in their molecules of several functional groups -COOH, NH2 - azote primary, secondary, tertiary, are able to coordinate metal ions. Examples are porfinic system. This tetradentate macromolecules. Schematically looks like this: (Picture 9)

Picture 9 Nitrogen donor atoms are located on square corners, tightly coordinated in space. Therefore porfinic form stable complex compounds with the metal. Thus, as the central atom can act Mg2+, Fe2+ forms an active center of hemoglobin. Protein molecule of 400 polypeptide chains forms globin. Each connected globin a gem. In the six iron atoms coordinating ties. 4 keeps it in the plane porfinic nucleus, and 2 are directed perpendicular to this plane. One of them is communication with oxygen. 10 000 atoms form a hemoglobin3082O870N760S8Fe4 Which means several similar carbon chains connect to donor atoms of nitrogen in a closed cycle. Different R radicals. Known BIOCOMPLEXES of other metals (Cu, Al, Si, Mn) Some of them find room in the medical practice as drugs. Feramid - a complex of iron chloride with nicotinic acid amides Fe (C6H5CONH2) Cl2 obalt porfin complex is part of B12, which plays an important role in the development and formation of red blood cells, its deficiency leads to pernicious anemia. Metal-gem properties depend on the occurance of toxic substances such as CO (carbon monoxide) and HCN - cyanides, salts of strong acids. When inhaled CO forms. Metal complex compounds - carbonyl hemoglobin 45

HbCO, stability constants are 200 times more than HbO2. So even a small amount of CO & quot; foresee &quot; significantly share deoxyhemoglobine. As a result, access of oxygen to the organs decreases, manifesting signs of hypoxia. A similar mechanism of action of cyanide, but their toxic effect is higher.High toxicity attributed high resistance connection Fe = CN-, which causes higher resistance cyanide hemoglobin. Toxic effects of copper compounds from the fact that copper ions interact with tiols-SH groups and amino - NH2 (blocking) proteins. This can be caused by bioclastic chelate type, resulting in proteins becoming insoluble, losing enzymatic activity, disrupting vital functions. Toxic effects of silver compounds from the fact that silver ions interact with toxic sulphur and nitrogen-containing proteins (nucleic acids).Similarly, there are compounds of gold. Toxicity increases with atomic number in the series. Property Metal ions form strong ties with sulphurligands used in the selection of proteins, which are used in poisoning. Such drugs are called - antidote.

H H H H C C C H S S H H + HgCl2 H H H

H C C C H S S SO3Na Hg

+ HCl

SO3Na

Chelating agent used as antidotes. Hg, Cd which are complex toxines in the body and are destroyed easily. Metalic-oligands homeostasis is a form of general homeostatic system. The body has a clear self-regulatory system homeostasis play elements in compounds with biooligands. Their level in the blood, tissue homeostasis is supported by regulatory mechanisms: absorption processes, separation of water, electrolytes and non-electrolytes, constant stability of chelates. Poor absorption of heavy metals is a consequence of the formation of slightly soluble complexes. Often abnormal digestive processes or change causes a violation of homeostasis. There are many ways of metaloligands regulation of homeostasis. So for Cu, Co, Fe, Zn the basic way is to change the level of absorption of cadmium and iodine - a selection from the urine of metal complexes. Harmful substances excreted from the body through bioligand that connects, tie them into complexes (helatotherapia). Many chemical elements with bioligand positively affect immunogenesis (protective reaction), increases the formation of antitoxins. According to Yatsymirskiy`s quote; complexing agents are an organisms life.

46

TOPIC 6: Preparation of the solutions and calculation of its concentrations.

The concentration of a solution is a macroscopic property, represents the amount of solute dissolved in a unit amount of solvent or of solution, and can be expressed in a variety of ways (qualitatively and quantitatively). (Table 6.1) Temperature Dependence of Several Concentration Expressions Concentration expression percent composition (by mass) molarity molality mole fraction Measurements required mass of solute mass of solution moles of solute volume of solution moles of solute mass of solvent moles of solute moles of solvent Molarity Molar concentration Molarity (in units of mol/l, molar, or M) or molar concentration denotes the number of moles of a given substance per liter of solution. A capital letter M is used to abbreviate units of mol/l. For instance: The actual formula for molarity is: Temperature dependent? No (mass does not change with temperature) Yes (volume changes with temperature) No (neither mass nor moles changes with temperature) No (moles does not change with temperature) Table 6.1

Such a solution may be described as "0.50 molar." It must be emphasized a 0.5 molar solution contains 0.5 moles of solute in 1.0 liter of solution. This is not equivalent to 1.0 liter of solvent. A 0.5 mol/l solution will contain either slightly more or slightly less than 1 liter of solvent because the process of dissolution causes volume of liquid to increase or decrease. Following the SI system of units, the National Institute of Standards and Technology, the United States authority on measurement, considers the term molarity and the unit symbol M to be obsolete, and suggests instead the amount-of-substance concentration (c) with the units mol/m3 or other units used alongside the SI such as mol/l. Preparation of a solution of known molarity involves adding an accurately weighed amount of solute to a volumetric flask, adding some solvent to dissolve it, then adding more solvent to fill to the volume mark. When discussing molarity of minute concentrations, such as in pharmacological research, molarity is expressed in units of millimolar (mmol/l, mM, 1 thousandth of a molar), micromolar (mol/l, M, 1 millionth of a molar) or nanomolar (nmol/l, nM, 1 billionth of a molar). Although molarity is by far the most commonly used measure of concentration, particularly for dilute aqueous solutions, it does suffer from a number of disadvantages. Masses can be determined with great precision as balances are often very precise. Determining volume is often not as precise. In addition, due to a thermal expansion, molarity of a solution changes with temperature without adding or removing any mass. For non-dilute solutions another problem is the molar volume of a substance is itself a function of concentration so volume is not strictly additive. Molarity tells us the number of moles of solute in exactly one liter of a solution. (Note that molarity is spelled with an "r" and is represented by a capital M.) We need two pieces of information to calculate the molarity of a solute in a solution: The moles of solute present in the solution. The volume of solution (in liters) containing the solute. 47

To calculate molarity we use the equation:

Molarity is probably the most commonly used unit of concentration. It is the number of moles of solute per liter of solution (not necessarily the same as the volume of solvent!). Example: What is the molarity of a solution made when water is added to 11g CaCl2 to make 100 mL of solution? Solution:

Molality Molality (mol/kg, molal, or m) denotes the number of moles of solute per kilogram of solvent (not solution). For instance: adding 1.0 mole of solute to 2.0 kilograms of solvent constitutes a solution with a molality of 0.50 mol/kg. Such a solution may be described as "0.50 molal". The term molal solution is used as a short hand for a "one molal solution", i.e. a solution which contains one mole of the solute per 1000 grams of the solvent. Following the SI system of units, the National Institute of Standards and Technology, the United States authority on measurement, considers the unit symbol m to be obsolete, and suggests instead the term 'molality of substance B' (mB) with units mol/kg or a related unit of the SI. This recommendation has not been universally implemented in academia yet. Note: molality is sometimes represented by the symbol (m), while molarity by the symbol (M). The two symbols are not to be confused, and should not be used as symbols for units. The SI unit for molality is mol/kg. (The unit m - not italicized - means meter.) Like other mass-based measures, the determination of molality only requires a good scale, because masses of both solvent and solute can be obtained by weighing, and molality is independent of physical conditions like temperature and pressure, providing advantages over molarity. In a dilute aqueous solution near room temperature and standard atmospheric pressure, molarity and molality will be very similar in value. This is because 1 kg of water roughly corresponds to a volume of 1 l at these conditions, and because the solution is dilute, the addition of the solute makes a negligible impact on the volume of the solution. However, in all other conditions, this is usually not the case. Molality, m, tells us the number of moles of solute dissolved in exactly one kilogram of solvent. (Note that molality is spelled with two "l"'s and represented by a lower case m.) We need two pieces of information to calculate the molality of a solute in a solution: The moles of solute present in the solution. The mass of solvent (in kilograms) in the solution. To calculate molality we use the equation:

Because the density of water at 25C is about 1 kilogram per liter, molality is approximately equal to molarity for dilute aqueous solutions at this temperature. This is a useful approximation, but remember that it is only an approximation and doesn't apply when the solution is at a different temperature, isn't dilute, or uses a solvent other than water. Example: What is the molality of a solution of 10 g NaOH in 500 g water? Solution: 48

Mole fraction The mole fraction , (also called molar fraction) denotes the number of moles of solute as a proportion of the total number of moles in a solution. For instance: 1 mole of solute dissolved in 9 moles of solvent has a mole fraction of 1/10 or 0.1. Mole fractions are dimensionless quantities. (The mole percentage or molar percentage, denoted "mol %" and equal to 100% times the mole fraction, is sometimes quoted instead of the mole fraction.) This measure is used very frequently in the construction of phase diagrams. It has a number of advantages: - the measure is not temperature dependent (such as molarity) and does not require knowledge of the densities of the phase(s) involved - a mixture of known mole fraction can be prepared by weighing off the appropriate masses of the constituents - the measure is symmetrical: in the mole fractions =0.1 and =0.9, the roles of 'solvent' and 'solute' are reversed. As both mole fractions and molality are only based on the masses of the components it is easy to convert between these measures. This is not true for molarity, which requires knowledge of the density. The mole fraction, X, of a component in a solution is the ratio of the number of moles of that component to the total number of moles of all components in the solution. To calculate mole fraction, we need to know: The number of moles of each component present in the solution. The mole fraction of A, XA, in a solution consisting of A, B, C, ... is calculated using the equation:

To calculate the mole fraction of B, XB, use:

This is the number of moles of a compound divided by the total number of moles of all chemical species in the solution. Keep in mind, the sum of all mole fractions in a solution always equals 1. Example: What are the mole fractions of the components of the solution formed when 92 g glycerol is mixed with 90 g water? (molecular weight water = 18; molecular weight of glycerol = 92) Solution:

It's a good idea to check your math by making sure the mole fractions add up to 1: Mass percentage (fraction) It has been suggested that Percentage solution be merged into this article or section. (Discuss) Mass percentage denotes the mass of a substance in a mixture as a percentage of the mass of the entire mixture. (Mass fraction w can be used instead of mass percentage by dividing mass percentage to 100.) Commercial concentrated aqueous reagents such as acids and bases are often 49

labeled in concentrations of weight percentage with the specific gravity also listed. In older texts and references this is sometimes referred to as weight-weight percentage (abbreviated as w/w% or wt%). In water pollution chemistry, a common term of measuring total mass percentage of dissolved solids in an aqueous medium is total dissolved solids. Mass-volume percentage Mass-volume percentage, (sometimes referred to as weight-volume percentage or percent weight per volume and often abbreviated as % m/v or % w/v) describes the mass of the solute in g per 100 mL of the resulting solution. Mass-volume percentage is often used for solutions made from a solid solute dissolved in a liquid. For example, a 40% w/v sugar solution contains 40 g of sugar per 100 mL of resulting solution. Volume-volume percentage Main article: Volume percent Volume-volume percentage (sometimes referred to as percent volume per volume and abbreviated as % v/v) describes the volume of the solute in mL per 100 mL of the resulting solution. This is most useful when a liquid - liquid solution is being prepared, although it is used for mixtures of gases as well. For example, a 40% v/v ethanol solution contains 40 mL ethanol per 100 mL total volume. The percentages are only additive in the case of mixtures of ideal gases. Volume Percent (% v/v) Volume percent or volume/volume percent most often is used when preparing solutions of liquids. Volume percent is defined as: Note that volume percent is relative to volume of solution, not volume of solvent. For example, wine is about 12% v/v ethanol. This means there are 12 ml ethanol for every 100 ml of wine. It is important to realize liqud and gas volumes are not necessarily additive. If you mix 12 ml of ethanol and 100 ml of wine, you will get less than 112 ml of solution. As another example. 70% v/v rubbing alcohol may be prepared by taking 700 ml of isopropyl alcohol and adding sufficient water to obtain 1000 ml of solution (which will not be 300 ml). Percent Composition (by mass) We can consider percent by mass (or weight percent, as it is sometimes called) in two ways: The parts of solute per 100 parts of solution. The fraction of a solute in a solution multiplied by 100. We need two pieces of information to calculate the percent by mass of a solute in a solution: The mass of the solute in the solution. The mass of the solution. Use the following equation to calculate percent by mass:

This is the mass of the solute divided by the mass of the solution (mass of solute plus mass of solvent), multiplied by 100. Example: Determine the percent composition by mass of a 100 g salt solution which contains 20 g salt. Solution: Normality Normality highlights the chemical nature of salts: in solution, salts dissociate into distinct reactive species (ions such as H+, Fe3+, or Cl-). Normality accounts for any discrepancy between the concentrations of the various ionic species in a solution. For example, in a salt such as MgCl2, there are two moles of Cl- for every mole of Mg2+, so the concentration of Cl- is said to be 2 N (read: 50

"two normal"). Further examples are given below. It may also refer to the concentration of a solute in any solution. The normality of a solution is the number of gram equivalent weight of a solute per liter of its solution. The definition of normality depends on the exact reaction intended. For example, hydrochloric acid (HCl) is a monoprotic acid and thus has 1 mol = 1 gram equivalent. One liter of 1 M aqueous solution of HCl acid contains 36.5 grams HCl. It is called 1 N (one normal) solution of HCl. It is given by the following formula:

In contrast, for sulfuric acid, which is diprotic acid, 2 N is usually 1 M, but may be defined as 2 M if pH < 2, where the once-deprotonated species, hydrogen sulfate, does not deprotonate. Normality is equal to the gram equivalent weight of a solute per liter of solution. A gram equivalent weight or equivalent is a measure of the reactive capcity of a given molecule. Normality is the only concentration unit that is reaction dependent. Example: 1 M sulphuric acid (H2SO4) is 2 N for acid-base reactions because each mole of sulphuric acid provides 2 moles of H+ ions. On the other hand, 1M sulphuric acid is 1N for sulphate precipitation, since 1 mole of sulphuric acid provides 1 mole of sulphate ions. Dilutions You dilute a solution whenever you add solvent to a solution. Adding solvent results in a solution of lower concentration. You can calculate the concentration of a solution following a dilution by applying this equation: where M is molarity, V is volume, and the subscripts i and f refer to the initial and final values. Example: How many millilieters of 5.5 M NaOH are needed to prepare 300 ml of 1.2 M NaOH? Solution:

So, to prepare the 1.2 M NaOH solution, you pour 65 mL of 5.5M NaOH into your container and add water to get 300 ml final volume. Preparing Chemical Solutions Lab experiments and types of research often require preparation of chemical solutions in their procedure. We look at preparation of these chemical solutions by weight (w/v) and by volume (v/v). The glossary below cites definitions to know when your work calls for making these and the most accurate molar solutions. To this we add information designed for understanding how to use the pH scale when measuring acidity or alkalinity of a solution. Glossary, basic terms to understand... Solute - The substance which dissolves in a solution Solvent - The substance which dissolves another to form a solution. For example, in a sugar and water solution, water is the solvent; sugar is the solute. Solution - A mixture of two or more pure substances. In a solution one pure substance is dissolved in another pure substance homogenously. For example, in a sugar and water solution, the solution has the same concentration through out, ie. it is homogenous. Mole - A fundamental unit of mass (like a "dozen" to a baker) used by chemists. This term refers to a large number of elementary particles (atoms, molecules, ions, electrons, etc) of any substance. 1 mole is 6.02 1023 molecules of that substance. (Avogadro's number).M Introduction to preparation of solutions. 51

Many experiments involving chemicals call for their use in solution form. That is, two or more substances are mixed together in known quantities. This may involve weighing a precise amount of dry material or measuring a precise amount of liquid. Preparing solutions accurately will improve an experiment's safety and chances for success. Solution 1: Using percentage by weight (w/v) Formula The formula for weight percent (w/v) is: Example A 10% NaCl solution has ten grams of sodium chloride dissolved in 100 ml of solution. Procedure Weigh 10g of sodium chloride. Pour it into a graduated cylinder or volumetric flask containing about 80ml of water. Once the sodium chloride has dissolved completely (swirl the flask gently if necessary), add water to bring the volume up to the final 100 ml. Caution: Do not simply measure 100ml of water and add 10g of sodium chloride. This will introduce error because adding the solid will change the final volume of the solution and throw off the final percentage. Solution 2: Using percentage by volume (v/v) When the solute is a liquid, it is sometimes convenient to express the solution concentration as a volume percent. Formula The formula for volume percent (v/v) is: [Volume of solute (ml) / Volume of solution (ml)] x 100 Example Make 1000ml of a 5% by volume solution of ethylene glycol in water. Procedure First, express the percent of solute as a decimal: Multiply this decimal by the total volume: Subtract the volume of solute (ethylene glycol) from the total solution volume: Dissolve 50ml ethylene glycol in a little less than 950ml of water. Now bring final volume of solution up to 1000ml with the addition of more water. (This eliminates any error because the final volume of the solution may not equal the calculated sum of the individual components). Solution 3: Molar Solutions Molar solutions are the most useful in chemical reaction calculations because they directly relate the moles of solute to the volume of solution. Formula The formula for molarity (M) is: moles of solute / 1 liter of solution or gram-molecular masses of solute / 1 liter of solution. Examples The molecular weight of a sodium chloride molecule (NaCl) is 58.44, so one gram-molecular mass (=1 mole) is 58.44 g. We know this by looking at the periodic table. The atomic mass (or weight) of Na is 22.99, the atomic mass of Cl is 35.45, so 22.99 + 35.45 = 58.44. If you dissolve 58.44g of NaCl in a final volume of 1 liter, you have made a 1M NaCl solution, a 1 molar solution. Procedure To make molar NaCl solutions of other concentrations dilute the mass of salt to 1000ml of solution as follows: 52

Asolution is a homogeneous mixture of a solute and a solvent. Solutions can be formed in any state of matter; that is they may be solid, liquid, or gas. A solution is prepared by dissolving a solute into the solvent. Solute is either the smaller component of a mixture or, when liquid solutions are considered, the gaseous or solid substance added to the solution. Solutions could be composed of either complete molecules - molecular solution, or ions - ionic solution. The latter usually is referred to aqueous solutions of salts. Fluids that mix or dissolve in each other in all proportions are call miscible fluids, lacking that property fluids are called immiscible. So gases are always miscible. The number of grams of solute that can just be dissolved in 100 ml of solvent at 20C is defined as the solubility (36g for NaCl). At the maximum solubility the solution is saturated and in dynamic equilibrium with the unsoluble part of solute. Such a solution is called saturated. Solution with less concentration is call unsaturated. (Picture 6.1)

Picture 6.1 NaCl(s) Na+(aq) + Cl-(aq) If there is more solute dissolved than saturation allows, the solution is said to be supersaturated. Supersaturated solutions are not in equilibrium with the solid substance. If a small crystal of sodium thiosulfate is added to a supersaturated solution of sodium thiosulfate, the excess immediately crystallizes out. Factors affecting solubility include intermolecular forces, viscosity, and entropy. Solubility varies dramatically. General 'rule' - "like dissolves like". The solubility of a solute in a solvent (that is, the extent of the mixing of the solute and solvent species) depends on a balance between the natural tendency for the solute and solvent species to mix and the tendency for a system to have the lowest energy possible. Molecular solutions. Intermolecular forces between the same molecules in comparison with others. For example, VdW only interacting molecules and those with hydrogen bonding. I alcoholes, their miscibility with water declines with increasing length of a hydrocarbon chain. Ionic solutions. Interacting between ion and water molecule is due an ion-dipole force. The attraction of ions for water molecules is called hydration. Hydration of ions can favor the dissolving of an ionic solid in water. That would be when energy of hydration of both ions exceeds the lattice energy which works against the solution process; ionic solids with relatively large lattice energy are usually insoluble. Remember that: Lattice energy ~ (charge x charge)/distance The smaller the size and the greater the charge on ions - the gretaer is the lattice energy. Compare it solubility table. 53

The solubility of a solute in both molecular solutions and ionic solutions is dependent on temperature and pressure. Temperature. Most gases are less soluble at high T but solid compounds usually (but not always) are more soluble with T. Heat of solution could be either positive or negative. Depending on that - different applications. Dissolving of ammonium nitrate in water is the basis for instant cold packs used in hospitals and elsewhere (NH4NO3 crystals inside a bag of water). When the inner bag is broken, NH4NO3 dissolves in the water. Heat is absorbed, so the bag feels cold. Similarly, hot packs are available, containing either CaCl2, MgSO4 or sodium acetate, which dissolve in water with the evolution of heat. Pressure. In general, pressure change has little effect on the solubility of a liquid or solid in water, except for gases. . Le Chatelier's principle - when a system in equilibrium is disturbed (by a change of temperature, pressure, or concentration variable), the system shifts in equilibrium composition in a way that tends to counteract this change of variable. CO2(g) --> CO2(aq) solubility increases with P. Henry's law: the solubility of a gas is directly proportional to the partial pressure of the gas above the solution, S = kHP , where S is the solubility of the gas (expressed as mass of solute per unit volume of solvent), kH is Henry's law constant for the gas for a particular liquid at a given temperature, and P is the partial pressure of the gas. Methods of expressing concentration of solution The most commonly used ways of expressing such solution concentration. 1. Mass fraction a ratio of the mass of the solute mx (g) solution to the mass msolution: Units of mass fraction - percentage or in parts. Mass of the solution related to the volume and density: where - the mass of the solution in g; V volume of solution in ml; density of the solution in g/ml. Mass of the solution can be termed as the sum of the masses of water and solute mass:

2. Molar concentration of - is the amount of solute per unit volume of solution: express then where, weight of the substance in g V volume of solution in liters. Units mol/l or mmol/l. From the formula of the molar concentration can find a lot of dissolved substances or hitch:

3. But the substance does not react in a molar ratio, and the equivalent. Equivalent - a particle of a substance X, which is equivalent to one proton and one electron. To find the equivalent it is necessary to know the equivalence factor feqv. - A number that indicates how the particle substance X is equivalent to one proton and one electron. Equivalence factor is given by: 54

where z is found for each class of compounds: a) z for acid - is the number of protons, which is replaced by a metal: For example, f eqv.(HCl) = ; f eqv.(H2SO4) = or , if replaced only by one

proton. b) z for a reason this number oxygroup: For example, f eqv.(NaOH) = ; feqv.(a(OH)2) = ;

c) z for salt - is the total valence of the metal (the product valence of the metal to its number): For example, f eqv. (Na2SO4) = ; f eqv.(Al2(SO4)3) = ;

d) z for the oxidation - reduction reactions this is the number of electrons, which gives a reducing or oxidizing agent accepts: For example, for the reaction Fe+2 1 Fe+3 feqv(Mn+7) = . feqv (Fe+2) = ;

for the reaction of Mn+7 +5e = Mn+2

Using an equivalence factor, molar mass equivalent can be calculated: Knowing the molar mass equivalent, we can calculate the molar concentration equivalent Cfekv.x (formerly the normal concentration of CN) - is the equivalent amount of a substance per unit volume of solution: where mx mass of the substance in g V volume of solution in liters. The units mol/l or mmol/l. From the formula of the molar concentration equivalent we can find a lot of dissolved substances or hitch: 4.Molarity concentration bX- number of substances in x 1kg solvent: Units mol/kg solvent. 5. The titer of the solutiont - a mass of solute in 1 ml of solution: Units g/ml. 6. To calculate the concentration of the solutions according to the titration use the law of equivalents - the product of molar solution concentration on the volume of the solution is of constant: 7. To calculate the concentration of solutions using the formula that bind different ways of expressing concentration: ;

55

TOPIC 7: The basic concepts of volumetric analysis. Neutralization method. Base Standardization.
What Is Volumetric Analysis? Quantitative chemistry is a branch of science that studies and differentiates matter in a chemical and molecular level using laboratory tests and equipments to show visible results. Volumetric analysis is one of the laboratory tests used in quantitative chemistry to show the relationship of a molecule's composition and the way they react to substances. It is also called volumetric titration because all experiments under this method of analysis are completed by titration reactions. Volumetric Analysis Volumetric analysis is a method of determining chemical differences and principles of redox (reduction-oxidation) reactions between molecules. Chemicals under this topic are classified based on the results obtained from titration. Titration The process of creating a balance chemical equation 'in vitro' is called titration. It typically uses a volumetric flask, hence, called volumetric titration. There are three types of volumetric titration, which are classified based on the rate of their reaction. Direct titration method (DTM) is a one-step titration process. Indirect method (ITM) involves a two-step titration process. Back titration method (BTM) uses a three-step titration process. Principle The principle involved in all titration methods is to balance a chemical reaction, such as achieving acid and base equilibrium. The most important key is to attain the desired end point regardless of the steps involved in the process. Therefore, it doesn't matter if it is processed using direct, indirect or back titration method because they will still arrive at the same equivalent point. ColorChange Titration starts by preparing two solutions, the analyte and titrant. Add an indicator to your analyte, and then slowly add your titrant solution in a drop-wise manner until the analyte changes its color. Analyte An analyte is a weak base or acid. Its structure is made from any compound that can be converted to a strong acid or base. Titrant The titrant is a strong acid or base that is slowly added to the analyte until it reaches any visible change in the color of the solution under observation. End Point Image 2 - pH of Body Fluids End Point This is your hint to know if the analyte has reached the minimum amount that is allowed to react with the titrant. Indicator It is a pH marker added to the analyte that triggers a change in color when equilibrium is reached. It should have a weaker acid/base concentration than the analyte.

56

Significance Volumetric analysis is applied to laboratory tests for analyzing and explaining the unknown chemical changes taking place inside our body. It is the test for understanding the complex patterns of amino acids and its DNA-related behaviors. Saponification (soap-making), extraction and standardization process also undergo titration methods. These are just a few from the endless list of volumetric analysis' applications and significance. Types of titrations There are various sorts of titrations whose goals are different to the others. The most common types of titrations in qualitative work are acid-base titrations and redox titrations. Acid-base titration Indicator Methyl Violet Bromophenol Blue Methyl Orange Methyl Red Litmus Bromothymol Blue Phenolphthalein Alizarin Yellow Main article: Acid-base titration Range of Color Color on Acidic Side Change Yellow 0.0 - 1.6 Yellow 3.0 - 4.6 Red 3.1 - 4.4 Red 4.4 - 6.2 Red 5.0 - 8.0 Yellow 6.0 - 7.6 Colorless 8.3 - 10.0 Yellow 10.1 - 12.0 Color on Basic Side

Violet Blue Yellow Yellow Blue Blue Pink Red Table 7.1 These titrations are based on the neutralization reaction that occurs between an acid and a base, when mixed in solution. The acid (resp. base) is added to a burette which was rinsed with the same acid prior to this addition to prevent contamination or diluting of the acid being measured. The base (resp. acid) is added to a volumetric flask which had been rinsed with distilled water prior to the addition to prevent contamination or dilution of the base/alkali being measured. The solution in the volumetric flask is often a standard solution; one whose concentration is exactly known. The solution in the burette, however, is the solution whose concentration is to be determined by titration. The indicator used for such an acid-base titration often depends on the nature of the constituents as described in the above section. Common indicators showing their colours, and the pH range in which they change colour, are given in the table above. When more precise results are required, or when the titration constituents are a weak acid and a weak base, a pH meter or a conductance meter ais used. (Table 7.1) Redox titration These titrations are based on a redox reactions between an oxidizing agent and a reducing agent. The oxidizing agent (resp. reducing agent) is added to the burette which was rinsed with the same oxidizing agent. The reducing agent (resp. oxidizing agent) is added to the conical flask, which had been rinsed with distilled water. Like in an acid-base titration, the standard solution is often the one in the conical flask, and the solution whose concentration is to be determined is the one in the burette. The procedure for carrying out redox titrations is similar to that required for carrying out acid-base titrations. Most commonly, a potentiometer or a redox indicator are used to determine the end point of the titration. For example, when one of constituents of the titration is the oxidizing agent potassium dichromate, the colour change of the solution from orange to green is not definite and thus an indicator such as sodium diphenylamine is used. The analysis of wines for their sulfur dioxide content requires the use of iodine as an oxidizing agent. In this case, starch is used as an indicator; a blue starch-iodine complex is formed once an excess of iodine is present, thus signalling the endpoint of the titration. On the other hand, some redox titrations do not require an indicator, due to the intense colour of some of the constituents. For instance, in a titration where the oxidizing agent potassium 57

permanganate (permanganometry) is present, a slight faint persisting pink colour signals the endpoint of the titration, and no particular indicator is therefore required. Complexometric titration These titrations are based on the formation of a complex between the analyte and the titrant. The chelating agent EDTA is very commonly used to titrate metal ions in solution. These titrations generally require specialized indicators that form weaker complexes with the analyte. A common example is Eriochrome Black T for the titration of calcium and magnesium ions. Measuring the endpoint of a titration Different methods to determine the endpoint include: pH indicator: This is a substance that changes colour in response to a chemical change. An acidbase indicator (e.g., phenolphthalein) changes colour depending on the pH. Redox indicators are also frequently used. A drop of indicator solution is added to the titration at the start; when the colour changes the endpoint has been reached. A potentiometer can also be used. This is an instrument that measures the electrode potential of the solution. These are used for titrations based on a redox reaction; the potential of the working electrode will suddenly change as the endpoint is reached. pH meter: This is a potentiometer that uses an electrode whose potential depends on the amount of H+ ion present in the solution. (This is an example of an ion-selective electrode.) This allows the pH of the solution to be measured throughout the titration. At the endpoint, there will be a sudden change in the measured pH. It can be more accurate than the indicator method, and is very easily automated. Water Two thirds of our body weight is water. Most biochemical reactions occur in aqueous solutions. Water molecules are polar and can interact with one another via hydrogen bonds. Water acts as a solvent by forming hydrogen bonds with other electronegative atoms (oxygen or nitrogen). Water molecules can dissociate (slightly) HOH H+ + OHDissociation constant:

In pure water [H+] = [OH-] = 10-7 and since the molarity of water is relatively constant at 55.6M in most solutions considered in biochemical problems, then we can define a new constant, the ion product of water: In all aqueous solutions, this equilibrium for the ionization of water must be fulfilled. Bronsted Acids and Bases. A Bronsted acid is a substance that donates protons (H+). A Bronsted base is a substance that accepts protons (H+). HA H++ A- where HA is the acid and A- is its conjugate base. The species formed by the ionization of an acid is its conjugate base. The species formed by the protonation of a base is its conjugate acid. Strong versus Weak Acids. A strong acid (HCl) dissociates completely, while a strong base (NaOH) readily picks up a proton. A weak acid (CH3COOH) barely dissociate. Equilibrium Constants and the Dissociation of Acids 58

Many biochemical reactions are reversible and do not proceed to completion. They do come to an apparent equilibrium or stop at a point between 0 and 100% completion. At equilibrium, the absolute velocity of the reaction in the forward direction equals the absolute velocity of the reaction in the reverse direction and the net velocity equals zero. The position of the equilibrium is described by an equilibrium constant Keq. For the dissociation of a weak acid the equilibrium constant is HA H+ + AIf Ka >>l, then the acid is a strong acid If Ka <<1, then the acid is a weak acid Definition of pH: The pH of a solution is a measure of its concentration of H+ (hydrogen ions To calculate pH from the concentration of hydrogen ions use the equation: How do you calculate the pH of strong and weak acids? 1. A strong acid is completely dissociated in solution, so the [H+] is equal to the concentration of the acid. 2. A weak acid is barely dissociated in solution, so the calculation of its pH is different. equal to the concentration of the weak acidand since we consider the solution to be electrically neutral, from this equation you can get the [H+] and calculate the pH. Definition of pKa: The pKa of an acid is the pH at which it is half dissociated. It can be experimentally determined by a titration curve which is a plot of the dependence of the pH of the solution on the amount of base (OH-) added to the solution. Neutralization and titration of strong acids and bases Remember that strong acids are completely dissociated in solution. Therefore the number of moles (equivalents) of base (OH-) required to neutralize the acid equals the number of moles (equivalents) of acid (H) present. Equivalents and Normality: One equivalent of an acid or base is the weight that contains I mole of replaceable H+ or OH-. The equivalent weight of a substance , where MW is the molecular weight of the substance and n is the number of replaceable H+ or OH-. The relationship between molarity (moles per liter) and normality (equivalents per liter) is Example: How many milliliters (mls) of0.025M H2S04 are required to neutralize 525 ml of 0.06 N KOH?

Titration of HCl (strong acid) by 1 M NaOH (strong base) (Picture 7.1) 1. 100 mls of O.lM HCI = 10 mmolesHCI. Starting 59

2. Addition of 9mmoles NaOH (9ml) neutralizes all but 1mmole of HCI 3. Addition of 9.9 mmoles NaOH neutralizes all but 0.1 mmole HCI Picture 7.1 4. Addition of 10 mmoles NaOH neutralizes all 10 mmoles HCI. pH = 7.0 Titration of a Weak Acid (CH3COOH) Picture 7.2 The weak acid-base conjugate pair resists changes in pH and therefore acts as a buffer. In the vicinity of the pKa, adding a large amount of base or acid produces little change in pH. In general, a weak acid is most effective in buffering against pH changes in the vicinity of its pKa.

Picture 7.2 Buffering Range: region of titration curve where pH change slowly (from pKa -1 to pKa +1). The importance of buffers in the body: Most enzymes that catalyze biochemical reactions are very pH sensitive. Consequently, body fluids must be protected against changes in pH and this protection mechanism must always be active because acids and bases are continually being produced by metabolic processes. The body is protected against pH changes by two main buffering systems (hemoglobin and the bicarbonate system) which maintain blood pH between 7.37 and 7 43. These systems work with mechanisms in the kidneys for excreting protons and mechanisms in the lungs for exhaling CO2 to maintain blood pH in the normal range. The bicarbonate buffering system depends on the fact that the carbon dioxide produced in fuel oxidation combines with water to make the carbonic acid,a weak acid. The carbonic acid partially dissociates into its conjuate base bicarbonate: CO2 + H2O H2CO3 HCO3- + H+ The H2CO3 /HCO3- acid-base pair acts as buffer. If you breathe more deeply and eliminate more CO2, you can drop the levels of carbonic acid and counteract an influx of acid in the body (metabolic acidosis) by shifting the equilibrium away from the II (compensatory respiratory alkalosis). In an opposite way, if the blood pH rises (metabolic alkalosis), by breathing more shallowly, CO2 is retained and the blood pH decreases (H+ increases) (compensatory respirator) acidosis). The Henderson-Hasselbaeh Equation (describes the relationship between pH and pKa) To derive start with the dissociation constant of a weak acid multiply by 1/Ka and then by 1/[H+] to get then take the log10 of both sides then this becomes pH = pKa + log [A-]/ [HA] Henderson Hasselbach Equation To calculate the pH of a solution of weak acid you need to know (I) the molar proportion of A(base) to HA (acid), and (2) the pKa of the acid. Calculation of points on a titration curve using the Henderson-Hasselbaeh equation.

60

Theory: When a weak acid is titrated by a strong base, the weak acid dissociates in solution to yield a very small amount of H+ ions. When OH- ions are added, they are neutralized by the H+ ions to form water. The removal of the H+disturbs the equilibrium between the weak acid and its ions. As a result, more HA dissociates to reestablish the equilibrium. The newly produced H+ ions can then be neutralized by more OH- and so on until all of the H+ originally present is neutralized. The overall result is represented by HA + OH- H2O + HThe number of equivalents of OH- required for complete neutralization is equal to the number of equivalents of hydrogen ion present as H+ and HA. Titration of 500 mls of a 0.1M weak acid (Ka = 10-5, pKa = 5) with a 0.1M strong base (KOH) 1. The starting pH depends on [HA] and pKa 2. What is the pH after you add 100 mls of 0.1M KOH? First, calculate how many moles HA are present: 0.5 liter x 0.1M 0.05 moles HA Second, calculate how many moles of OH- are added: 0.1 liter x 0.1M =0.01 moles OHHA H++ AStarting conditions: 0.05 Change: 0.05-0.01 0.01 + (adding 0.01 moles OH will titrate an equal amount of H+ ions and pull the equilibrium to the right, increasing the [A-] and decreasing the [HA] by 0.01). At New Equilibrium: pH pKa + log [A-]/[HA] = 5 +log0.01 moles (500 + 100mls) 0.04 moles (500 + 100mls) = 5 +log (0.01/0.04) = 5 + (-0.6) =4.40 = pH 3. What is the pH after you add 250 mls of 0.1M KOH? (1) 0.05 moles of HA are present and (2) 0.250 liters x 0.1M = 0.025 moles OH- added. HA H++ AStarting conditions: Change At Now Equilibrium: 0.05 0.05-0.025 0.025 pH = pKa + log [A-]/[HA] = 5 + log 0.025 moles/(500 + 250 mls) 0.025 moles/(500 + 250 mls) pH = 5 + log I =5 + 0 = 5

4. What is the pi I after you add 375 mis 0.1M KOH? (1) 0.05 moles of HA are present and (2) 0.375 liters x 0.1M = 0.0375 moles OH- added HA H++ AStarting conditions: 0.05 Change: 0.05-0.0375 0.0375 At New Equilibrium: pH = pKa + log [A-l/[HA] = 5 + log 0.0375molcs (500 + 375 mls) 0.0125moles (500 + 375 mls) pH = 5 + log 3 = 5 + 0.48 = 5.48 Titration Endpoint: The pH at the endpoint of the titration of a weak acid is not 7 because A-, the conjugate base of HA, ionizes (A-+ HOH HA + OH-). This is an equilibrium reaction which does not go to completion. [A-] at the endpoint = 500 mls x 0.1M =0.05 moles in (500 ml + 500 ml) = 0.05M We must use some new terms to calculate:

61

Acid-Base Indicators
Indicator A weak acid or weak base that changes colour upon protonation/deprotonation, i.e. its conjugate is a different colour. Let's look at the reactions indicators undergo: HIn + H2O In- + H3O+
acid colour base colour

or In + H2O HIn+ + OH+

base colour acid colour

For the first case, we can write the equilibrium expression as

Solving for [H3O+] gives

You get the acid colour when

You get the base colour when

Take log of both sides

acid colour when base colour when VOLUMETRIC ANALYSIS Volumetric or titrimetric analysis is based on an accurate measurement of the volume of titrant spent in the reaction with the substance under investigation. Titrated solution is called with exactly known concentration. The initial call substances that can prepare a solution of accurate weigh. 62

Indicators are weak organic acids or bases that change their color depending on the pH of the solution. The interval transition color indicator this pH range in which the indicator changes its color.(Table 7.2) Color in the acidic Transition interval Color in the alkaline Indicator environment color (pH) environment Methyl orange ink 3,1 4,4 yellow Phenolphthalein Colourless 8,2 10,5 raspberry Methyl red Red 4,2 6,2 yellow Litmus Red 58 blue Table 7.2 The method of neutralization Neutralization method - a method of volumetric analysis, which uses volumetric solution of acids and alkalis. The method is based on neutralization reaction: H+ + OH H2O. Depending on the method of neutralization of the titrant, is divided into alkalimetry and acidimetry. Alkalimetry a method for determination of acids and salts, which give the hydrolysis of an acid reaction, using volumetric solution of alkali. Titrant bases NaOH and KOH are preparing for a rough hitch, and then establish their title, the exact concentration of precursor oxalate (oxalic acid) N2S2O4 2H2O and succinate (succinic acid) NOOS CH2CH2COOH alkaline solutions are prepared at about the same concentration as the starting material, a sample of alkali calculated, knowing the concentration of the original substance. Acidimetric a method of determining the bases and salts, which give the hydrolysis of alkaline reaction, with the help of titrant acid. Titrant acid HCI and H2SO4 are prepared for a rough hitch, and then they establish their titre, the exact concentration of precursor sodium carbonate Na2CO3, sodium tetra borate (borax)Na2B4O7 10H2O and sodium oxalate Na2S2O4. Acid solutions are prepared about the same concentration as the starting material, sample of the acid is calculated knowing the concentration of the substance. HELATOMETRY Chelatometry is a method of volumetric analysis, which uses titrant complexing. Complexones amino polycarbonic acids and their derivatives. Increasingly using ethylenediaminetetraacetic acid (Trilon B), which is to give chelates metal cations:

Picture 7.3 To determine the end of the titration using indicators - Black T, blue chromogen, murexid. The chemistry of the method: Ind + Me blue Me-Ind + TrB 63 Me-Ind; cherry Me-TrB + Ind

cherry The starting materials of the method: MgO; CaCO3, Zn.

red

METHOD OF PERMAGANATION Permanganation- a method of volumetric analysis, which uses potassium permanganate titrant KMnO4. The main reaction is the method: MnO4 + 8H+ + 5 Mn+2 +4H2O KMnO4 titrant is prepared for a rough hitch, and then set the title of the original substance H2C2O4 or Na2C2O4. Titration is carried out in an acidic medium. End of titration set for the appearance of pink color when adding one extra drop of solution KMnO4. METHOD OF IODOMETRY Iodometry - a method of volume analysis, which uses titrant I2 or I . The basic equation of the method: I2 + 2 2I Since the titration of iodine is slow, then to the test solution we added an excess of iodine, and the residue titrated sodium thiosulphate Na2S2O3: 2 Na2S2O3 + I2 2NaI + Na2S4O6. The precursor method I2. Titration is carried out in acidic or neutral media. Indicator is starch. End of titration is set by the disappearance of blue color of iodine with starch.

64

TOPIC 8: Neutralization method. Acid Standardization.

Acids and bases have been known by their properties since the early days of experimental chemistry. The word "acid" comes from the Latin acidus , meaning "sour" or "tart," since water solutions of acids have a sour or tart taste. Lemons, grapefruit, and limes taste sour because they contain citric acid and ascorbic acid (vitamin C). Another common acid is vinegar, which is the sour liquid produced when apple cider, grape juice, or other plant juices ferment beyond the formation of alcohol. Vinegar is a 5 percent water solution of acetic acid. Besides having a sour taste, acids react with active metals to give hydrogen, they change the colors of indicators (for example, litmus turns from blue to red), and they neutralize bases. Bases change the colors of indicators (litmus turns from red to blue) and they neutralize acids. Hence, bases are considered the chemical opposite of acids. Most common acid-base reactions take place in water solutions (commonly referred to as aqueous solutions). One of the earliest definitions of acids, advanced by the Swedish physicist and chemist Svante Arrhenius in 1887, stated that acid ionizes in aqueous solution to produce hydrogen ions (which are protons), H+, and anions; and a base ionizes in aqueous solution to produce hydroxide ions (OH) and cations. Later studies of aqueous solutions provided evidence of a small, positively charged hydrogen ion combining with a water molecule to form a hydrated proton, H+(H2O) or H3O+, which is called the hydronium ion. Often, the hydronium ion or hydrated proton is represented as H+ (aq). Hydrogen chloride (HCl), a gas, is an acid because it dissolves in water to yield hydrogen ions and chloride ions. This water solution of HCl is referred to as hydrochloric acid. A typical base, according to the Arrhenius definition, is sodium hydroxide (NaOH). It dissolves in water to give sodium ions and hydroxide ions. In the reaction of an acid with a base in aqueous solution, the hydrogen ions of the acid react with the hydroxide ions of the base to give water. The second product is a salt, which is composed of the positive metal ion from the base and the negative ion from the acid. For example, HCl (aq) + KOH ( aq ) H2O (l) + KCl ( aq ) Since HCl (aq) and KOH (aq) are fully ionized in solution, the preceding equation can be written as H+ (aq) + Cl (aq) K+ (aq) + OH (aq) Ions common to both sides can be canceled to yield H2O (l) K+ (aq) + Cl (aq)

H+ (aq) + OH (aq) H2O This is referred to as the net ionic equation for the neutralization reaction. If H3O+ is substituted for H+ ( aq ), the neutralization equation becomes H 3O + (aq) + OH (aq) 2H2O

Acidity and Alkalinity A common method to determine whether a substance is acid or alkaline, is by the use of litmus paper. Litmus is a soluble powder obtained from lichens. It is also available in solution form. It is used merely as an indicator of acidity or alkalinity, it will not show the relative strength of either condition. It indicates the condition by a change in color. The litmus paper comes in two colors. 1. Red, which is used to test for an alkali, if the substance is alkaline the paper will turn blue. 2. Blue, which is used to test for acid, if the substance is acidic the paper will turn red. If the paper does not change color the substance is neutral (pH7). To indicate relative acid or alkali strength a universal indicator must be used. Universal indicators are available as paper strips or as solutions. The solutions will give a full spectrum of color changes, from red (acid) through to purple (alkaline). Each kit will contain a color matching chart which indicates the relative strength of the acid or alkaline condition. 65

REACTION MEDIUM WATER SOLUTIONS pH Water - a weak electrolyte - dissociates by the equation: H2O H+ + OH Ionic product of water - a product of the concentration of hydrogen ions (protons) on the concentration of hydroxide ions: It is a constant at a given temperature. Dissociation of acids follows the scheme: CH3COOH H+ + CH3COO Active acidity - is a concentration drowned. Potential acidity - is a concentration dissociating acid molecules. Total acidity - is the total concentration of acid in the mole eq. The amount of active and potential acidity equal to the total acidity. When the titration is determined by the total acidity. Total alkalinity - is the concentration of hydroxide - anions. Potential alkalinity - is the concentration of undissociated molecules of the base. Total alkalinity - is the total concentration of alkali in the mole eq. The amount of active and potential alkalinity equal total alkalinity. When the titration is determined by the total alkalinity. The reaction medium is determined by the concentration of protons.
10-1 acid condition 10-7 neut condition alkaline condition 10-14

Concentration of protons in an acid solution is calculated by the formula: strong acid =1 trong base =1

acid degree of dissociation The dissociation of the base form of hydroxide anions, whose concentration is calculated as follows: strong base strong base =1 =1

base degree of dissociation The reaction medium is more convenient to express the solution via the pH. pH - is the negative logarithm of hydrogen ion concentration: Similarly, we can calculate the pOH: Based on the negative logarithm of the ion product of water is: blood pH = 7.36; gastric juice pH = 0,9 - 1,5.

66

TOPIC 9: Acid-base equilibrium in human body. pH of biological liquids.

Lets consider an acid, HA, in water.The Brnsted-Lowry acid/base theory states that, the acid must protonate the water to form hydronium and the conjugate base, A-. An equilibruim will form between the acid and water, and hydronium and the conjugate base. HA + H2O H3O+ + AThis equilibrium can be utilized to calculate the concentrations of species in the solution contents Acid Dissociation Constant Like all equilibria, an acid/base dissociation will have a particular equilibrium constant which will determine the extent of the reaction (whether it lies to the left or right of the equation). Strong acids/bases dissociate completely, so their equilibrium constants are overwhelmingly large. Because the equilibrium is used for calculating the concentrations of weak acids, only little water reacts. The concentration of water during the reaction is, therefore, a constant, and can be excluded from the expression for K. This gives rise to a unique equilibrium constant, Ka, known as the acid dissociation constant. Which is simply K multiplied by the concentration of water. The Ka of a weak acid determines how acidic it is, i.e., how far its equilibrium lies to the right. The Ka values of weak acids can and have been determined experimentally. Base Dissociation Constant A similar equilibrium exists when a weak base is dissolved in water. The base will accept a proton from water and form a conjugate acid, BH+. B + H2O OH- + BH+ This equilibrium has its own unique constant, Kb, which is known as the base dissociation constant. Like the acid dissociation constant, it is termed as the equilibrium constant multiplied by the concentration of water. Ion Product Constant A unique equilibrium exists between normal water molecules. At times, one water molecule will act as an acid, and donate a proton to another water molecule (which acts as a base). This is the auto-ionization of water.

H2O + H2O H3O- + OHIn accordance with the Le Chatelier Principle, we can clearly see that if the hydronium ion concentration is increased (by adding an acid), the equilibrium will move to the left and there will be a lower concentration of hydroxide. Thus, hydronium and hydroxide concentration are inversely relatedan increase in one will lead into in a decrease in the other, and vice versa. The equilibrium expression for this reaction has a special name,which is Kw. This is because it simplifies the product of hydronium and hydroxide concentration, it is sometimes called the ion product constant. The value of this constant is 1.0 10-14 at 25C. This expression can be used to obtain the pH of pure water. Note that the pH is the negative logarithm of hydronium ion concentration. If we set the hydronium ion concentration in the above expression to be x, we can find the pH. The hydroxide ion concentration must also be x (since each molecule of hydroxide is a result of a molecule of hydronium forming). We have:

67

This technique can be used to determine the pH of any solution if either one of the ion concentrations are known. Conjugate Base Expressions The conjugate bases of weak acids have a relationship with their parent acids. Consider the equilibrium expression of the conjugate base, A-, of the weak acid HA. If we multiply the expression for an acid by the expression for its conjugate base, the concentrations of the acid and conjugate base cancel and we obtain the ion product constant for water! This allows us to calculate the Kb of a base if the Ka of it's conjugate acid is known (and vice versa).

Summary The definitions of the acid and base dissociation constants are very important. They are presented here for reference. The acid dissociation constant measures the strength of an acid dissolved in water. The base dissociation constant measures the strength of a base dissolved in water. The ion product constant relates the concentrations of acids/bases and their conjugates in a solution.

pH Regulation in the Human Body Acid base imbalance resulting from the metabolic production of organic acids is common and potentially life threatening. Plasma acid-base status is a good measure of the whole body's acid-base balance. The bicarbonate buffer system is the major buffer of plasma and interstitial fluids The acid in this buffer system is CO2, even though it is really an acid anhydride CO2 + H2O Equilibrium: [H2O] is constant so we can eliminate it from the equation. In clinical labs, pH and PCO2 arc measured and [HCO3-] is calculated using the Hcndcrson Hassclbach equation...how does PCO2 fit into this equation? The concentration of a gas in solution is proportional to its partial pressure the equilibrium constant becomes: and the Henderson-Hasselhach equation becomes: with [HCO3-] expressed in meq I/1 Why is the bicarbonate buffer system (pKa of 6.1) effective in buffering in a pll range far from its pKa? Because it is an open system where the PCO2 is adjusted to meet the body's needs. 68 H2CO3,

As strong acid is added, [HCO,-] diminishes and CO, is formed. But excess CO, is exhaled so that the ratio of [HCO3-] does not change dramatically. And when astrong base is added, it will beneutralized by carbonic acid, but CO, will be replaced metabolically and the f [HCO3-] ratio will not change dramatically. What disorders in the acid base balance would you seen as physicians? Respiratory acidosis: Caused by alveolar hypoventilation and accumulation of CO2, in body, occurs when respiration depth or rate decreases as seen in airway obstruction, neuromuscular disorders, diseases of the central nervous system or in chronic obstructive lung diseases like emphysema. Respiratory alkalosis: Arises from decreased alveolar PCO2 and is most commonly found as the result of hyperventilation due to anxiety. Also can be caused by salicylate poisoning, fever, artificial ventilation, and high altitude (since there is a decrease in total atmospheric pressure and therefore alveolar PCO2). Metabolic acidosis: Caused by disorders in which excess lactic acid, acetoacetic acid or phydroxy butyric acid are produced, or ingestion of salicylates, ethylene glycol, or methyl alcohol all of which produce strong organic acids. Metabolic alkalosis We cannot synthesized alkaline materials from neutral starting materials, so metabolic alkalosis must be caused by intake of excess alkali (sodium bicarbonate) orr abnormal loss of acid (prolonged vomiting). Acid-base equilibria in biological systems The most essential solvent in chemistry is water. Almost all the chemical reaction between acid and base and salts take place in water solutions. However water itself is not an acid nor base, fot the reason that the species that determine the acidity (H+) and basicity (OH-) are present H2O H+ + OH- dissociation reaction for water But in the T=22 C only 1 of 10 million (10-7) molecules of water dissociates. As a result there10-7 ions of H+ and there10-7 ions of OH-. The ionic product of water is the product of concentrations of [H+] [OH-] ions. [H+] [OH-]=10-7 10-7 =10-14 const For the pure water the concentrations of [H+] = [OH-] = 10-7. If we add acid to the water conc of + [H ] increases [H+]>10-7, to keep the ionic product of water permanent the conc of [OH-] decreases. Example: [H+] = 10-3>10-7 than 10-14= [H+] [OH-] =10-3X X=10-14 -10-13 =10-11 The same thing will be with the conc of [OH-] if alkaline solution is added [OH-] = 10-5>10-7 than 10-14= [H+] [OH-] =10-5X X=10-14 -10-5 =10-9 If the conc of one ion goes up the conc of another must go down proportionally to satisfy the equation [H+] [OH-] =10-14 Thus we can calculate the conc of [H+] knowing [OH-]. The acidity and basicity can be interpreted through the [H+] or [OH-], but in practice we use [H+] more often. If [H+]= 10-7 the mediun is neutral [H+]>10-7 the mediun is acidic [H+]<10-7 the mediun is basic

69

The ion conc are very small that is why Sorensen proposed new coefficient for acidity pHnegative logarithm based on 10 of the [H+] conc. Strength Hydroxyl ions 10-14 10-13 10-12 10-11 10-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 100 pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Hydrogen ions 100 10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9 10-10 10-11 10-12 10-13 10-14 Common Substances Sulphuric Acid Hydrochloric Acid Lemon Juice/vinegar Wine of beer Human Scin Rain water Distilled water Ethanol/blood Sea water Milk of magnesia Lime water Ammonia Lye A L K A L I N E Table 9.1

Strong Acid ACID

Weak Acid Neutral Weak Alkali

Strong Alkali

70

TOPIC 10: Buffer systems, classification and mechanism.

Buffers a solution that tends to resist changes in pH as a result of dilution or the addition of small amounts of acids or bases. In practice, its a solution where the weak acid and its conjugate base (e.g., acetic acid and sodium acetate) or a weak base and its conjugate acid (e.g., ammonia and ammonium chloride) are present. Buffers are formed when: 1 A weak acid is titrated by a strong base 2 A weak base is titrated by a strong acid 3 A weak acid is combined with a salt containing its conjugate base. 4 A weak base is combined with a salt containing its conjugate acid. If the weak acid HA, and NaA (the sodium salt of its conjugate base) are both dissolved in water, two equilibria are established:

HA + H2O A- + H2O

A- + H3O+ HA + OH-

The resulting solution may be acidic, neutral or basic, depending upon which equilibrium predominates. (Dominates means that equilibrium is favored to the right as written.) If Ka dominates (has a larger value), the solution is acidic. If Kb dominates (hes a larger value), the solution is basic. Lets start by assuming that we can decouple these reactions:

Usually, CHAand CA are big (0.1M) compared to Ka or Kb or Kw, so these values of [H3O+] and [OH-] are very small compared to CHA and CA, so that they can be ignored; these equations then simlify to: Therefore, if we rewrite the expression for Ka as and then (-log) of both sides:

The Henderson Hasselbalch equation Lets do an example from the book. What is the pH of a solution that is 0.400M in formic acid (HCOOH) and 1.00 M in sodium formate (HCOONa)? 1) First, lets find out if it will be acidic or basic: HCOOH +H2OH3OHCOO- + H2O HCCOH + OHKa = 1.80 10-4

71

[HCOO-]CHCOO

[HCOOH] CHCOOH

2) Then, using Henderson Hasselbalch we can calculate:

Recall that we used Henderson Hasselbalch in Expt.2:

pH

Volume of NaOH added (ml.) Effects of dilution on pH of a buffered solution, a weak acid and a strong acid Take home lessons: 1) The effective pH range of a buffer is pH pKa1 2) A buffers pH is resistant to dilution, until [HA] Ka 3) A buffer has a capacity to resist change in pH upon addition of acids or bases. BUFFER SYSTEMS State the buffer systems, which steadfastly maintain the pH by adding small amounts of strong acid or alkali, as well as dilution There are two types of buffer systems: a) Acid consisting of a weak acid and its salts are formed strong bases. Example, acetate buffer: CH3COOH + CH3COONa. b) Base consisting of a weak base and its salts, formed strong acid. For example, an ammonia buffer: NH4OH + NH4Cl. Basic equations of the buffer systems acid type Henderson's equation Gasselbaha acid type where Buffering capacity - the number mole equivalents of strong acid or strong base to be added to 1 liter buffer system to shift the pH to 1. Buffer capacity determined by titration. Formulas for calculating the buffer capacity: by acid 72 by alkaline basic type basic type

73

The buffer capacity is the measure of magnitude on buffer action. Buffer solution is one which maintains fairly constant pH, even when small amounts on alkali are added to it. A buffer may be acidic buffer or basic buffer. Acidic buffer obtained by mixing weak acid with salt of the same acid. The basic buffer made mixing a weak base with a salt of the same weak base. It should be definite as the number of moles of an acid (or a base) which when supplementary to a litre of buffer solution modify its pH by unity.Therefore, Buffer capacity = (No.of moles of acid added) / (Numerical value of change in pH) Example: When 0.01 mole of HCl should be additional to a buffer that enclose 1 mole each of acetic acid and sodium acetate, its pH revolutionize by 0.01 unit. Then its buffer capacity will be, Buffer capacity = {0.01 (mole of HCl)} / {0.01 {change in pH)}= 1.0 A buffer has utmost buffer capacity when; Buffer mixtures are very widely employed for preparing standard pH solutions. These are employed for determining pH of an unknown solution by colorimetric method. Buffer capacity play significant role in agriculture. Actually, the carbonates, bicarbonates and phosphates, present in the soil, that act as buffers. Due to microbiological activity, organic acids are also product in the soil. These acids, being weak, act as excellent buffering agents. Most biological secretions or fluids like blood, milk and so on, possess definite pH values. Similarly, presence of organic acids carbonates or bicarbonates in the animal systems maintain proper pH of their fluids. Acetic acid-sodium acelate buffer is used in the taking away of phosphate, throughout the qualitative inorganic study of the mixtures. Buffer solution is able to retain almost constant pH when small amount of acid/base is added. Quantitative measure of this resistance to pH changes is called buffer capacity. Buffer capacity can be defined in many ways. You may find it defined as maximum amount of either strong acid or strong base that can be added before a significant change in the pH will occur. This definition - instead of explaining anything - raises a question what is a significant change? sometimes even change of 1 unit doesn't matter too much, sometimes - especially in biological systems - 0.1 unit change is a lot. Buffer capacity can be also defined as quantity of strong acid or base that must be added to change the pH of one liter of solution by one pH unit. Such definition although have its practical applications - gives different values of buffer capacity for acid addition and for base addition (unless buffer is equimolar and its pH=pKa). This contradicts intuition - for a given buffer solution its resistance should be identical regardless of whether acid or base is added. Buffer capacity definition that takes this intuition into account is given by where n is number of equivalents of added strong base. Note that addition of dn moles of acid will change pH by exactly the same value but in opposite direction. We will derive formula connecting buffer capacity with pH, pKa and buffer concentration. To make further calculations easier let's assume that the strong base added is monoprotic, we also assume volume of 1 which will allow us to treat concentration and number of moles interchangeably. Charge balance of the solution is given by the equation [B+] is nothing else but concentration of the strong base present (or - as a volume is 1 - number of moles of strong base present) in the solution - thus it is n from 1 definition. Total concentration of the buffer, Cbuf, is given by From dissociation constant definition we have so 74

TOPIC 11: Buffer capacity. The role of buffer solutions in biological systems.

or

Or equations 1,2 and water ionization constant definition when combined give us formula for the amount of the strong base:

How Buffers Work: A Quantitative View The kidneys and the lungs work together to help maintain a blood pH of 7.4 by affecting the components of the buffers in the blood. Therefore, to understand how these organs help control the pH of the blood, we must first discuss how buffers work in solution. Acid-base buffers confer resistance to a change in the pH of a solution when hydrogen ions (protons) or hydroxide ions are added or removed. An acid-base buffer typically consists of a weak acid, and its conjugate base (salt) (see Equations 2-4 in the blue box, below). Buffers work because the concentrations of the weak acid and its salt are large compared to the amount of protons or hydroxide ions added or removed. When protons are added to the solution from an external source, some of the base component of the buffer is converted to the weak-acid component (thus using up most of the protons added); when hydroxide ions are added to the solution (or, equivalently, protons are removed from the solution; see Equations 8-9 in the blue box, below), protons are dissociated from some of the weak-acid molecules of the buffer, converting them to the base of the buffer (and thus replenishing most of the protons removed). However, the change in acid and base concentrations is small relative to the amounts of these species present in solution. Hence, the ratio of acid to base changes only slightly. Thus, the effect on the pH of the solution is small, within certain limitations on the amount of H+ or OH- added or removed. The Carbonic-Acid-Bicarbonate Buffer in the Blood By far the most important buffer for maintaining acid-base balance in the blood is the carbonicacid-bicarbonate buffer. The simultaneous equilibrium reactions of interest are H+(aq) + HCO3-(aq) H2CO3(aq) H2O(l) + CO2(g)

We are interested in the change in the pH of the blood; therefore, we want an expression for the concentration of H+ in terms of an equilibrium constant (see blue box, below) and the concentrations of the other species in the reaction (HCO3-, H2CO3, and CO2). Recap of Fundamental Acid-Base Concepts An acid is a chemical species that can donate a proton (H+), and a base is a species that can accept (gain) a proton, according to the common Brnstead-Lowry definition. Hence, the conjugate base of an acid is the species formed after the acid loses a proton; the base can then gain another proton to return to the acid. In solution, these two species (the acid and its conjugate base) exist in equilibrium. (2) + where [H ] is the molar concentration of protons in aqueous solution. When an acid is placed in water, free protons are generated according to the general reaction shown in Equation 3. Note: HA and A- are generic symbols for an acid and its deprotonated form, the conjugate base.
acid base conjugate base

HA + H2O H3O+ + A(3) Equation 3 is useful because it clearly shows that HA is a Brnstead-Lowry acid (giving up a proton to become A-) and water acts as a base (accepting the proton released by HA). However, the nomenclature H3O+ is somewhat misleading, because the proton is actually solvated by many water molecules. Hence, the equilibrium is often written as Equation 4, where H2O is the base:
conjugate acid

75

HA

H+ + A-

(4)

Equilibrium Constant for an Acid-Base Reaction Using the Law of Mass Action, we can also define an equilibrium constant for the acid dissociation equilibrium reaction in Equation 4. This equilibrium constant, known as Ka, is defined by Equation 5: (5) Equilibrium Constant for the Dissociation of Water One of the simplest applications of the Law of Mass Action is the dissociation of water into H+ and OH- (Equation 6).

H2O(l) H+(aq) + OH-(aq)

(6)

The equilibrium constant for this dissociation reaction, known as Kw, is given by Kw = [H+][OH-] (7) (H2O is not included in the equilibrium-constant expression because it is a pure liquid.) Hence, we can see that increasing the OH- concentration of an aqueous solution has the effect of decreasing the H+ concentration, because the product of these two concentrations must remain constant at a given temperature. Thus, in water, the equilibrium in Equation 6 underlies the equivalency of the Brnstead-Lowry definition of a base (an H+ acceptor) and the Arrhenius definition of a base (an OH- producer). To more clearly show the two equilibrium reactions in the carbonic-acid-bicarbonate buffer, Equation 1 is rewritten to show the direct involvement of water:
acid-base reaction

H3

O+(aq)

+ HCO3-(aq) H2CO3(aq) + H2O(l) 2H2O(l) + CO2(g)

(8)

not an acid-base reaction

The equilibrium on the left is an acid-base reaction that is written in the reverse format from Equation 3. Carbonic acid (H2CO3) is the acid and water is the base. The conjugate base for H2CO3 is HCO3- (bicarbonate ion).Carbonic acid also dissociates rapidly to produce water and carbon dioxide, as shown in the equilibrium on the right of Equation 10. This second process is not an acidbase reaction, but it is important to the blood's buffering capacity, as we can see from Equation 9, below. (9) The derivation for this equation is shown in the yellow box, below. Notice that Equation 11 is in a similar form to the Henderson-Hasselbach equation presented in the introduction to the Experiment (Equation 16 in the lab manual). Equation 11 does not meet the strict definition of a Henderson-Hasselbach equation, because this equation takes into account a non-acid-base reaction (i.e., the dissociation of carbonic acid to carbon dioxide and water), and the ratio in parentheses is not the concentration ratio of the acid to the conjugate base. However, the relationship shown in Equation 10 is frequently referred to as the Henderson-Hasselbach equation for the buffer in physiological applications. In Equation 9, pK is equal to the negative log of the equilibrium constant, K, for the buffer (Equation 10). (10) where (from Equation 8). This quantity provides an indication of the degree to which HCO3- reacts with H+ (or with H3O+ as written in Equation 10) to form H2CO3, and subsequently to form CO2 and H2O. In the case of the carbonic-acid-bicarbonate buffer, pK=6.1 at normal body temperature. Derivation of the pH Equation for the Carbonic-Acid-Bicarbonate Buffer We may begin by defining the equilibrium constant, K1, for the left-hand reaction in Equation 10, using the Law of Mass Action: (11) (12) 76

(13) (14) (15) Because we are interested in the pH of the blood, we take the negative log of both sides of

where (from Equation 8).

As shown in Equation 11, the pH of the buffered solution (i.e., the blood) is dependent only on the ratio of the amount of CO2 present in the blood to the amount of HCO3- (bicarbonate ion) present in the blood (at a given temperature, so that pK remains constant). This ratio remains relatively constant, because the concentrations of both buffer components (HCO3- and CO2) are very large, compared to the amount of H+ added to the blood during normal activities and moderate exercise. When H+ is added to the blood as a result of metabolic processes, the amount of HCO3(relative to the amount of CO2) decreases; however, the amount of the change is tiny compared to the amount of HCO3- present in the blood. This optimal buffering occurs when the pH is within approximately 1 pH unit from the pK value for the buffering system, i.e., when the pH is between 5.1 and 7.1. However, the normal blood pH of 7.4 is outside the optimal buffering range; therefore, the addition of protons to the blood due to strenuous exercise may be too great for the buffer alone to effectively control the pH of the blood. When this happens, other organs must help control the amounts of CO2 and HCO3- in the blood. The lungs remove excess CO2 from the blood (helping to raise the pH via shifts in the equilibria in Equation 10), and the kidneys remove excess HCO3- from the body (helping to lower the pH). The lungs' removal of CO2 from the blood is somewhat impeded during exercise when the heart rate is very rapid; the blood is pumped through the capillaries very quickly, and so there is little time in the lungs for carbon dioxide to be exchanged for oxygen. The ways in which these three organs help to control the blood pH through the bicarbonate buffer system are highlighted in picture 11.1

Picture 11.1 This figure shows the major organs that help control the blood concentrations of CO2 and HCO3-, and thus help control the pH of the blood. Removing CO2 from the blood helps increase the pH. Removing HCO3- from the blood helps lower the pH. 77

Why the Optimal Buffering Capacity Is at pH=pK Why is the buffering capacity of the carbonic-acid-bicarbonate buffer highest when the pH is close to the pK value, but lower at normal blood pH? The answer to this question lies in the shape of the titration curve for the buffer, which is shown in Figure 4, below. Titration Curve for the Bicarbonate-Buffer System It is possible to plot a titration curve for this buffer system, just as you did for your solution in the acid-base-equilibria experiment. In this plot, the vertical axis shows the pH of the buffered solution (in this case, the blood). The horizontal axis shows the composition of the buffer: on the left-hand side of the plot, most of the buffer is in the form of carbonic acid or carbon dioxide, and on the right-hand side of the plot, most of the buffer is in the form of bicarbonate ion. Note that as acid is added, the pH decreases and the buffer shifts toward greater H2CO3 and CO2 concentration. Conversely, as base is added, the pH increases and the buffer shifts toward greater HCO3concentration (Equation 10). (Picture 11.2)
% buffer in the form of HCO3 8 7 pH 0 25 50 75 100 8 7

Normal blood pH Region of maximum buffering capacity

6 5

pK = 6.1

6 5

4 100

4 75 50 25 0

% buffer in the form of H2CO3 and CO2

Picture 11.2 This is the titration curve for the carbonic-acid-bicarbonate buffer. Note that the pH of the blood (7.4) lies outside the region of greatest buffering capacity (green). Note: The percent buffer in the form of HCO3- is given by the formula: The slope of the curve is flattest where the pH is equal to the pK value (6.1) for the buffer. Here, the buffering capacity is greatest because a shift in the relative concentrations of bicarbonate and carbon dioxide produces only a small change in the pH of the solution. However, at pH values higher than 7.1, the slope of the curve is much higher. Here, a shift in the relative concentrations of bicarbonate and carbon dioxide produces a large change in the pH of the solution. Hence, at the physiological blood pH of 7.4, other organs must help to control the amounts of HCO3- and CO2 in the blood to keep the pH relatively constant, as described above. Other pH-Buffer Systems in the Blood Other buffers perform a more minor role than the carbonic-acid-bicarbonate buffer in regulating the pH of the blood. The phosphate buffer consists of phosphoric acid (H3PO4) in equilibrium with dihydrogen phosphate ion (H2PO4-) and H+. The pK for the phosphate buffer is 6.8, which allows this buffer to function within its optimal buffering range at physiological pH. The phosphate buffer only plays a minor role in the blood, however, because H3PO4 and H2PO4- are found in very low concentration in the blood. Hemoglobin also acts as a pH buffer in the blood. That hemoglobin 78

protein can reversibly bind either H+ (to the protein) or O2 (to the Fe of the heme group), but that when one of these substances is bound, the other is released (as explained by the Bohr effect). During exercise, hemoglobin helps to control the pH of the blood by binding some of the excess protons that are generated in the muscles. At the same time, molecular oxygen is released for use by the muscles.

79

TOPIC 12: Colligative properties. Osmosis.

Colligative properties are properties of solutions that depend on the number of molecules in a given volume of solvent and not on the properties (e.g. size or mass) of the molecules.[1] Colligative properties include: lowering of vapor pressure; elevation of boiling point; depression of freezing point and osmotic pressure. Measurements of these properties for a dilute aqueous solution of a non-ionized solute such as urea or glucose can lead to accurate determinations of relative molecular masses. Alternatively, measurements for ionized solutes can lead to an estimation of the percentage of ionization taking place. Vapor pressure The relationship between the lowering of vapor pressure and concentration is given by Raoult's law, which states that: The vapor pressure of an ideal solution is dependent on the vapor pressure of each chemical component and the mole fraction of the component present in the solution. Boiling point and freezing point Both the boiling point elevation and the freezing point depression are proportional to the lowering of vapor pressure in a dilute solution Boiling point elevation Boiling Point total = Boiling Point solvent + Tb where Tb = molality Kb i, (Kb = ebullioscopic constant, which is 0.51C kg/mol for the boiling point of water; i = Van 't Hoff factor) Boiling point is achieved in the establishment of equilibrium between liquid and gas phase. At the boiling point, the number of gas molecules condensing to liquid equals the number of liquid molecules evaporating to gas. Adding any solute effectively dilutes the concentration of the liquid molecules, slowing the liquid to gas portion of this equilibrium. To compensate for this and reattain the equilibrium, boiling point is achieved at higher temperature. Any description of a colligative property which includes steric occlusion, or blocking of the surface to reduce the vapor pressure has no basis in reality, even despite this explanation being frequently taught. This is also why vapor pressure and boiling point are independent of a liquid's accessible surface area. Alternatively, measurements for ionized solutes can lead to an estimation of the percentage of ionization taking place. (Picture 12.1) Boiling point elevation and freezing point depression These effects are readily understood in terms of the schematic diagrams shown below. The red shading indicates the temperatures required to make equal numbers of microstates thermally accessible in the two phases.

80

Picture 12.1 Boiling Point Elevation We've already seen that in a solution, the vapour pressure of the solution is lowered. Thus, it is reasonable to conclude that one would have to raise the temperature of solution more to bring it to the boiling point. this point is well illustrated in the Phase diagram for water and solution figured above. There is a definite relationship between the concentration of solute and the increase in boiling point c.f. the pure liquid. (Picture 12.1)

kb = boiling point elevation constant for the liquid. We can use boiling point elevation measurements to determine the molar mass of an unknown solute. Example: A sample of 1.20 g of a non-volatile organic compound is dissolved in 60.0 g benzene. The BP of solution is 80.96C. BP of pure benzene is 80.08C. What is the molar mass of the solute.

but, we only have 60.0 g benzene, not 1000 g. so # moles solute = molality #kg solvent

Dilution of the solvent adds new energy states to the liquid, but does not affect the vapor phase. This raises the temperature required to make equal numbers of microstates accessible in the two phases. The shifts of the boiling- and and freezing points in opposite directions reflects the higher energies of vapor microstates and lower energies of solid microstates in relation to those of the liquid. Note that these diagrams are purely schematic and nowhere near to scale!

81

Picture 12.2 DTf = kf m where kf is the freezing point depression constant for the liquid and m is the molality of the solute. Example A solution of 2.95 g of sulfur in 100 g cyclohexane had a freezing point of 4.18C, pure cyclohexane has a fp of 6.50C. What is the molecular formula of sulphur? DTf = 6.5 - 4.18 = 2.32C kf = 20.2C kg mol-1 (look up in tables)

Example How much glycol (1,2-ethanediol), C2H6O2 must be added to 1.00 l of water so the solution does not freeze above -20C? kf (H2O) = 1.86C kg mol-1

since 1.0 l has a mass of 1.0 kg we need 10.8 mol of ethylene glycol

As mentioned previously, the more conventional explanation of bp elevation and fp depression is given in terms of vapor pressures. The latter are measures of the free energies of molecules in a phase, and the relationships are best understood by showing plots of TS for each phase in terms of the temperature:

82

G0

gas

solid liquid

solid
TM

liquid gas
TB T

Picture 12.3 Melting and boiling points of a pure substance. The stable phase at any temperature will be the one having the lowest free energy, and from which molecules have the smallest escaping tendency.
G0

gas

solid liquid

solid
TM

liquid
TM TB

gas
TB T

solution

f.p. depression

b.p. elevation

Picture 12.4 Melting- and boiling points of a solvent containing a non-volatile solute. The solute "dilutes" the solvent, reducing its free energy (purple line) and shifting the transition temperatures in opposite directions. Freezing point depression Freezing Pointsolution = Freezing Pointsolvent Tf where Tf = molality Kf i, (Kf = cryoscopic constant, which is 1.86C kg/mol for the freezing point of water,; i = Van 't Hoff factor) Freezing point, or the equilibrium between a liquid and solid phase is generally lowered in the presence of a solute compared to a pure solvent. The solute particles cannot enter the solid phase, hence, fewer molecules participate in the equilibrium. Again, re-establishment of equilibrium is achieved at a lower temperature at which the rate of freezing becomes equal to the rate of liquefying. (Picture 12.2) Osmotic pressure Two laws governing the osmotic pressure of a dilute solution were discovered by the German botanist W. F. P. Pfeffer and the Dutch chemist J. H. vant Hoff: The osmotic pressure of a dilute solution at constant temperature is directly proportional to its concentration. The osmotic pressure of a solution is directly proportional to its absolute temperature. 83

These are analogous to Boyle's law and Charles's Law for gases. Similarly, the combined ideal gas law, PV = nRT, has an analog for ideal solutions: V = nRTi where: = osmotic pressure; V is the volume; T is absolute temperature; n is the number of moles of solute; R = 8.3145 J K-1 mol-1, the molar gas constant; i = Van 't Hoff factor. Osmotic pressure is given the symbol P (Greek equivalent of P) and the equation relating the osmotic pressure to the amount of solute is: PV = nRT Note that n/V is concentration in mol/liter so we can also write P = Csolute RT P can be measured at room temperature and is therefore, more useful for measuring solutes which might decompose at higher (boiling point elevation) temperature measurements. It is also extremely sensitive to small amounts of solute and is therefore useful for measuring very large molar mass values. Example An aqueous solution containing 1.10 g of a protein in 100 ml of solution has an osmotic pressure of 3.93 10-3 atm at 25C. What is the molar mass of the protein? or in SI units

note that in this case, I used a different value for the ideal gas constant R=0.08203 L-atm/molK This is simply a convenience. The alternate way is to convert to SI units. The pressure on a liquid affects its volatility When a liquid is subjected to hydrostatic pressure for example, by an inert, non-dissolving gas that occupies the vapor space above the surface, the vapor pressure of the liquid is raised. The pressure acts to compress the liquid very slightly, effectively narrowing the potential energy well in which the individual molecules reside and thus increasing their tendency to escape from the liquid phase. (Because liquids are not very compressible, the effect is quite small; a 100-atm applied pressure will raise the vapor pressure of water at 25 C by only about 2 torr.) In terms of the entropy, we can say that the applied pressure reduces the dimensions of the "box" within which the principal translational motions of the molecules are confined within the liquid, thus reducing the density of the quantized energy states in the liquid phase. Why pressure affects the volatility of a liquid. Applying hydrostatic pressure to a liquid increases the spacing of its microstates, so that the number of energetically accessible states in the gas, although unchanged, is relatively greater thus increasing the tendency of molecules to escape into the vapor phase. In terms of free energy, the higher pressure raises the free energy of the liquid, but does not affect that of the gas phase. Osmotic flow and osmotic pressure Molecules in a fluid are always subject to random thermal motions. If a given kind of molecule is present in greater concentration in one region of a fluid, the effect of these random motions will be to produce a net migration into the region of lower concentration; this migration is known as thermal diffusion. Osmotic flow (commonly known simply as osmosis) occurs when molecules of a solvent diffuse through a membrane that is permeable only to those molecules, and into a solution in which the solvent is "diluted" by the presence of solute molecules. In the simplest example, there is pure solvent on the left side of the membrane; on the other side the same solvent contains a solute whose molecules are too large to pass through the membrane. Because the solvent concentration on the

84

right side will always be smaller than that on the left, osmotic flow will continue indefinitely if the right side can accommodate the increased volume. (Picture 12.6)

Picture 12.6 If, however, the liquid on the right side of the membrane is placed under hydrostatic pressure, the driving force for osmotic flow will diminish. If the pressure is raised sufficiently high, osmotic flow will come to a halt; the system is then said to be in osmotic equilibrium. The pressure required to bring about osmotic equilibrium (and thus to stop osmotic flow) is known as the osmotic pressure, commonly denoted by (Greek capital pi). (Picture 12.7)

Picture 12.7 Osmotic equilibrium, like any kind of equilibrium, occurs when the free energies (that is, the escaping tendencies) of the diffusible molecules are the same on the two sides of the membrane. The free energy on the right side, initially lower due to the lower solvent concentration, is raised by the hydrostatic pressure, making it identical with that of the pure liquid on the left. From the standpoint of microscopic energy states, the effect of the applied pressure is to slightly increase the spacing of solvent energy states on right side of the membrane so as to equalize the number of accessible states on the two sides, as shown here in a very schematic way. Osmosis in physiology and biochemistry Osmosis helps biological cells maintain their structure. Cell membranes are semipermeable and allow water, small molecules, and hydrated ions to pass, while blocking the passage ofbiopolymers synthesized inside the cell. The difference in concentrations of solutes inside and outside the cell gives rise to an osmotic pressure, and water passes into the more concentrated solution in the interior of the cell, carrying small nutrient molecules. The influx of water also keeps the cell swollen, whereas dehydration causes the cell to shrink. These effects are important in everyday medical practice. To maintain the integrity of blood cells, solutions that are injected into the bloodstream for blood transfusions and intravenous feeding must be isotonic with the blood,

85

meaning that they must have the same osmotic pressure as blood. If the injected solution is too dilute, or hypotonic, the flow of solvent into the cells, required to equalize the osmotic pressure, causes the cells to burst and die by a process called haemolysis. If the solution is too concentrated, or hypertonic, equalization of the osmotic pressure requires flow of solvent out of the cells, which shrink and die. Osmosis also forms the basis of dialysis, a common technique for the removal of impurities from solutions of biological macromolecules and for the study of binding of small molecules to macromolecules, such as an inhibitor to an enzyme, an antibiotic to DNA, and any other instance of cooperation or inhibition by small molecules attaching to large ones. In a purification experiment, a solution of macromolecules containing impurities, such as ions or small molecules (including small proteins or nucleic acids), is placed in a bag made of a material that acts as a semipermeable membrane and the filled bag is immersed in a solvent. The membrane permits the passage of the small ions and molecules but not the larger macromolecules, so the former migrate through the membrane, leaving the macromolecules behind. In practice, purification of the sample requires several changes of solvent to coax most of the impurities out of the dialysis bag. COLLIGATIVE PROPERTIES OF SOLUTIONS. OSMOSIS. CRYOMETRY. Colligation is known properties of solutions arising from thermal motion and the amount of kinetic particle system. Osmosis is a spontaneous one-sided diffusion of solvent through a semi permeable membrane toward a solution with higher concentration. Semipermeable membrane, which passes only the solvent molecules. Examples: natural animal and plant cell membranes, the intestinal wall; artificial colloid ion, cellophane, gelatin, parchment, clay wall of the vessel filled with sediment membrane. Osmotic pressure is the excess hydrostatic pressure, which stops osmosis. Osmotic concentration is the concentration of all the transport of particles of solute in solution. Law Van't Hoff - the osmotic pressure of a dilute electrolyte solution is equal to the gas pressure that would produce the solute, while in a gaseous state, occupying the volume of the solution at the same temperature. The equation of osmotic pressure for non-electrolytes: where C = concentration of solution in mol/l; R - universal gas constant, 0.082 l atm / g mol; T - temperature in Kelvin. Equation for osmotic pressure of electrolytes: where i- isotonic coefficient of van't Hoff. Isotonic coefficientVan't Hoff and shows how many times the osmotic pressure of the electrolyte, the osmotic concentration of the electrolyte is greater than the osmotic pressure and osmotic concentration of the non electrolyte, at the same molar concentration. Isotonic coefficient Van't Hoff related to the degree of dissociation equation: where - the number of ions in the electrolyte which dissociates. State the isotonic solutions with the same osmotic pressure. Hypotonic solution is called with small osmotic pressure. Hypertonic solution is called with a large osmotic pressure. Haemolysis is the destruction of the cell membrane by placing the cells in the hypotonic solution. Plasmolysis is wrinkling cells by placing it in the hypertensive solution. Turgor is the elastic state of the cell membrane. Osmotic blood pressure = 7.7 atm. Oncotic pressure of blood is part of the osmotic pressure caused by the HMC and is equal to 0.04 atm. 86

Osmotic pressure 1M solution of nonelectrolyte = 22.4 atm.

87