Brdy 6ed Ch13 MixturesAtTheMolecularLevel

Chapter 13:
Mixtures at the Molecular

Level: Properties of Solutions
Personal use only !!!
Chemistry: The Molecular Nature
of Matter, 6E
Jespersen/Brady/Hyslop
Sebagai seorang yang belajar kimia. Apa yang sama pada gambar di atas !!
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

A Look Ahead
• We begin by examining diferent types of solutons that can be
formed from the three states of mater: solid, liquid, and gas.
We also characterize a soluton by the amount of solute present
as unsaturated, saturated, and supersaturated.
(12.1)

• Next we study the formaton of solutons at the molecular
level and see how intermolecular forces afect the energetcs of
the soluton process and solubility. (12.2)
• We study the four major types of concentraton units—
percent by mass, mole fracton, molarity, and molality—and
their interconversions. (12.3)
• Temperature in general has a marked efect on the solubility of
gases as well as liquids and solids. (12.4)

A Look Ahead
• We see that pressure has no infuence on the solubility of liquids

and solids, but greatly afects the solubility of gases. The quanttatve
relatonship between gas solubility and pressure is given by Henry’s
law. (12.5)
• We learn that physical propertes such as the vapor pressure,
meltng point, boiling point, and osmotc pressure of a soluton

depend only on the concentraton and not the identty of the solute
present. We frst study these colligatve propertes and their
applicatons for nonelectrolyte solutons. (12.6)
• We then extend our study of colligatve propertes to electrolyte
solutons and learn about the inf uence of ion pair formaton on these
propertes. (12.7)
• The chapter ends with a brief examinaton of colloids, which are
partcles larger than individual molecules that are dispersed in
another medium. (12.8)

Chapter 13: Solutions
Solution
 Homogeneous mixture
 Composed of solvent and solute(s)
Solvent
 More abundant component of mixture
Solute(s)
 Less abundant or other component(s) of mixture
Ex. Lactated Ringer’s solution
 NaCl, KCl, CaCl2, NaC3H5O3 in water
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 5


Why do Solutions Form?
Two Driving Forces behind Formation of
Solution
1. Entropy/Disorder
2. Intermolecular Forces
Whether or not a solution forms depends on
both opposing forces

Spontaneous Mixing
 2 gases mix
spontaneously
 Due to random motions
 Mix without outside work

 Never separate
spontaneously
 Tendency of system
left to itself, to
become increasingly
disordered Gas A Gas B
 Entropy effect
separate mixed
Spontaneous Mixing
 Strong driving force in nature
 System, left to itself, will tend towards
most probable state
Gaseous Solutions

 Entropy only driving force
 Attractive (Intermolecular) forces negligible
Liquid Solutions
 Entropy is one driving force
 Attractive (intermolecular) forces are very
important

Intermolecular Forces (IMF)
 Attractive forces between solute and

solvent hold solution together
 Strength of intermolecular attractive forces

depends on both solute and solvent

Intermolecular Forces (IMF)
 Initially solute and solvent separate
 Solute molecules held together by IMFs
 Solvent molecules held together by IMFs
 When mixed, for solution to form,
 Solvent-to-solute attractions must be ≈
to attractions between solute alone and
solvent alone

Why Such Different Behavior?
 When liquids combine
1. Must put in Energy to overcome or lessen
intermolecular attractive forces between
molecules

 Must push solute molecules apart
 Must push solvent molecules apart

Why Such Different Behavior?
2. When solute and solvent mix or come
together
 Must form new intermolecular forces

between solute and solvent
 Releases energy

Miscible Liquids
Miscible liquids
 2 liquids that are soluble in each other
 Dissolve in one another in all proportions
 Form solution

 Strengths of intermolecular attractions
are similar in solute and solvent
 Similar polarity
Ex. Ethanol and water
H H  +
Ethanol;
H C C O H polar bond
H H
Immiscible Liquids
 Two insoluble liquids
 Do not mix
 Get two separate phases
 Strengths of IMFs are different in

solute and solvent
 Different polarity
Ex. Benzene and water H
H C H
Benzene; C C
no polar bond C C
H C H
H
Rule of Thumb
 “Like dissolves Like”
 Use polar solvent for polar solute
 Use Nonpolar solvent for nonpolar
solute

 When strengths of intermolecular
attractions are similar in solute and
solvent, solutions form because net
energy exchange is about the same

Process of Dissolution
 Polar solutes interact with
H3C CH 2
and dissolve in polar
solvents O H
 
 H-bonding solutes interact


with and dissolve in H-
bonding solvents H

O
H

Ex. Ethanol in water
 Both are polar molecules
 Both form hydrogen bonds
 IMFs of EtOH and H2O large
and similar
Ex. of Miscible Solution
 When ethanol dissolves in water, get H-bonding
 IMF of solution also large
 When solutions form, there will be enough
energy to move EtOH and H2O apart so can mix

 Solvent and solute are “similar” (IMF strength)
 Solution will form
H
H
O
H O H H
H3C O H O
C
H2 H H2C CH3
O
H
Process of Dissolution
 Non-polar solutes interact with and
dissolve in non-polar solvents
 Both have only London dispersion forces
 Why form solution?

 Put energy in to overcome IMFs between
molecules in solute and solvent
 When solute and solvent mix or come together,
form new IMFs between solute and solvent
 Releases ~ same amount of energy as
put in
Ex. Benzene in CCl4
 CCl4
 Nonpolar
 Weak London forces
 Benzene, C6H6

 Nonpolar
 Weak London forces
 Similar in strength to CCl4
 Small E to move apart
 Small E gained for solution IMFs
 Does dissolve, solution forms
Ex. of Immiscible Solution
Benzene in water
 Benzene
 Nonpolar
 Weak London dispersion forces only
 Water
 Polar
 Strong hydrogen bonding

Ex. of Immiscible Solution
Benzene in water
 Solvent and solute are very “different”
 Costs energy to break strong H-bonds in H 2O
 No strong IMFs in solution with benzene to
offset
 No solution forms
 2 layers, Don’t Mix

Learning Check
Which of the following are miscible in water?

Your Turn!
Which of the following molecules is soluble in
C 6H 6?
A. NH3
B. CH3NH2

C. CH3OH
D. CH3CH3
E. CH3Cl

Solutions of Solids in Liquids
 Basic principles remain the same when
solutes are solids
 Sodium chloride (NaCl)
 Ionic bonding

 Strong intermolecular forces
 Ions dissolve in water because ion-dipole forces
of water with ions strong enough to overcome
ion-ion attractions

Hydration of Solid Solute
 At edges, fewer
oppositely charged ions
around
 H2O can come in
 Ion-dipole forces

 Remove ion
 New ion at surface
 Process continues until
all ions in solution
 Hydration of ions
 Completely surrounded
by solvent

Hydration vs. Solvation
 Hydration
 Ions surrounded by water molecules
 Solvation
 General term for surrounding solute particle by
solvent molecules

 Do polar molecules dissolve in H2O?
 Yes
 Attractions between solvent and solute dipoles
(dipole-dipole interactions) dislodge molecules
from solid
 Bring into solution

Polar Molecule in Water
 H2O reorients so
 Positive Hs are near negative ends of solute
 Negative Os are near positive ends of solute

Solvation in Nonpolar Solvents?
 Wax and benzene
 Weak London dispersion forces in both
 Wax molecules
 Easily slip from solid

 Slide between benzene molecules
 Form new London forces between solvent and
solute

Heat of Solution
 Energy change associated with formation of
solution
 Difference in intermolecular forces between
isolated solute and solvent and mixture
 Cost of mixing
 Enthalpy exchanged between system and
surroundings
Molar Enthalpy of Solution (Hsoln)
 Amount of enthalpy exchanged when one
mole of solute dissolves in a solvent at
constant pressure to make a solution

Heat of Solution
 Hsoln > 0 (positive)
 Costs energy to make solution
 Endothermic
  PE of system
 H < 0 (negative)
soln
 Energy given off when solution is made
 Exothermic
  PE of system
 Which occurs depends on your system

Modeling Formation of Solution
Formation of solution from solid and liquid
can be modeled as 2-step process
 Step 1: Separate Solute and Solvent
molecules

 Break intermolecular forces
 Endothermic,  PE of system, “cost”
 Step 2: Mix Solute and Solvent
 Come together
 Form new intermolecular forces
 Exothermic,  PE of system, “profit”

2-Step Process
 Application of Hess’ Law
 Way to take 2 things we can measure and use
to calculate something we can’t directly measure
 Hsoln is path independent

 Method works because enthalpy is state function
 Hsoln = Hsoln – Hsolute – Hsolvent
Overall, steps take us from
solid solute + liquid solvent  final solution
 These steps are not the way solution
would actually be made in lab

Enthalpy Diagram
1. Break up solid lattice
 Hlattice = Lattice enthalpy
  PE
1. Dissolve gas in solvent 1
 HSolvation = Solvation

enthalpy
  PE
Hsolution = Hlattice + HSolvation
direct
 Whether Hsolution + or –
depends on values
 In lab, solution formed
directly
Fig 13.5 Dissolving KI in H2O
Hlattice (KI) = 632 kJ mol–1
Hhydration (KI) = – 619 kJ mol–1
Hsolution = Hlatt + Hhydr
Hsoln = 632 kJ mol–1
Personal use only !!! – 619 kJ mol–1

Hsoln = +13 kJ mol–1
 Formation of KI(aq) is
endothermic

Dissolving NaBr in H2O
Hlattice (NaBr) = 728 kJ mol–1
Hhydration (NaBr) = –741 kJ mol–1
Hsolution = Hlatt + Hhydr
Hsoln = 728 kJ mol–1
Personal use only !!! – 741 kJ mol–1

Hsoln = – 13 kJ mol–1
 Formation of NaBr(aq) is
exothermic

Your Turn!
 When 2.50 g of solid sodium hydroxide is added to
100.0 g of water in a calorimeter, the temperature
of the mixture increases by 6.5 oC. Determine the
molar enthalpy of solution for sodium hydroxide.
Assume the specific heat of the mixture is 4.184 J g -

1 K-1.
A. +44.6 kJ/mol
B. +43.5 kJ/mol
C. -44.6 kJ/mol
D. -43.5 kJ/mol
∆Hsoln = -(102.5 g)(4.184 J g-1 K-1)(6.5 K)
(1 kJ/1000J)/(2.5 g/40.0 g mol-1) = -44.6 kJ
Solutions Containing Liquid Solute
Similar treatment but
with 3 step path
1. Solute expanded to gas
 H +
  PE

1. Solvent expanded to
gas
 H +
  PE
1. Solvation occurs
 H –
  PE
Hsoln = Hsolute + Hsolvent + Hsolvation
Ideal Solution
 One in which inter-
molecular attractive
forces are identical
 Hsoln = 0
Ex. Benzene in CCl4

 All London forces
 Hsoln ~ 0
 Step 1 + Step 2 = –Step 3

 or
Hsolute + Hsolvent = –Hsolvation
Gaseous Solutes in Liquid Solution
 Only very weak attractions exist between
gas molecules
 There are no intermolecular attractions in ideal
gases

 When making solution with gas solute
 Energy required to “expand solute” is
negligible
 Heat absorbed or released when gas
dissolves in liquid has two contributions:
1. Expansion of Solvent Hsolvent
2. Solvation of Gas Hsolvation
Gaseous Solutes in Liquid Solution

 Gas dissolves in  Gas dissolves in H2O
organic solvent
 Exothermic (–)
 Endothermic
 Hsolvation < 0
 Hsolvation >0
Your Turn!
The solubility of a substance increases with

increased temperature if:
A. ΔHsolution >0
Personal use only

B. ΔHsolution <0
C. ΔH =0
solution
!!!

Solubility
 Mass of solute that forms saturated solution with
given mass of solvent at specified temperature
g solute
solubility=
100 g solvent
 If extra solute added to saturated solution, extra


solute will remain as separate phase

Effect of T on Solubility of Solids and
Liquids in Liquid Solvent
 If heat is absorbed when solute dissolves,
solubility  when T 
→
solute undissolved + energy ← solute dissolved
 If energy is released when solute dissolves,
Personal
solute
use
solute
only
solubility  when T 
+ energy
!!!
undissolved
→
← dissolved
 When apply “stress” to equilibrium (by  T),
equilibrium will shift so as to relieve (absorbs or
minimizes) stress
 LeChâtelier’s Principle

Solubility of Most Substances
Increases with Temperature
 Most substances
become more
soluble as T 
Personal use only !!!  Amount solubility 

 Varies considerably
 Depends on
substance

Effect of T on Gas Solubility in Liquids
 Solubility of gases usually  as T 
Table 13.2 Solubilities of Common Gases in Water

Case Study: Dead Zones
 During the industrial revolution, factories were
built on rivers so that the river water could be
used as a coolant for the machinery. The hot
water was dumped back into the river and cool

water recirculated. After some time, the rivers
began to darken and many fish died. The
water was not found to be contaminated by
the machinery. What was the cause of the
mysterious fish kills?
Increased temperature, lowered

amounts of dissolved oxygen
Effect of Pressure on Gas Solubility
 Solubility  as P 
Why?
  P means  V above
solution for gas

 Gas goes into
solution
 Relieves stress on
system
 Conversely, solubility
 as P 
 Soda in can

Effect of Pressure on Gas Solubility
A. At some P, equilibrium exists between vapor phase and
solution
 ratein = rateout
B.  in P puts stress on equilibrium
  frequency of collisions so ratein > rateout

 More gas molecules dissolve than are leaving solution
C. More gas dissolved
 Rateout will  until Rateout = Ratein and equilibrium
restored

Henry’s Law
 Pressure-Solubility Law
 “Concentration of gas in liquid at any given
temperature is directly proportional to partial
pressure of gas over solution”

Cgas = kHPgas (T is constant)
Cgas = concentration of gas
Pgas = partial pressure of gas
kH = Henry's Law constant
 Unique to each gas
 Tabulated
Henry’s Law
 True only at low concentrations and
pressures where gases do NOT react with
solvent
 Alternate form
Personal Puse
=
P
only !!! C1
1
C2
2
 C1 and P1 refer to an initial set of conditions
 C2 and P2 refer to a final set of conditions

Ex. 1 Using Henry’s Law
Calculate the concentration of CO2 in a soft drink that
is bottled with a partial pressure of CO 2 of 5 atm over
the liquid at 25 °C. The Henry’s Law constant for CO2
in water at this temperature is 3.12  102 mol/L·atm.

C CO =k H (CO 2 ) PCO
2 2
= 3.12  102 mol/L·atm * 5.0 atm

= 0.156 mol/L  0.16 mol/L
When under 5.0 atm pressure

Ex. 1 Using Henry’s Law
Calculate the concentration of CO2 in a soft drink
after the bottle is opened and equilibrates at 25 °C
under a partial pressure of CO2 of 4.0  104 ·atm.
C1 C2 P2 C1
= C 2=
P1 P2 P1
( 0 . 156 mol/L ) (4 . 0×10 atm ) −4

C 2=
5 .0 atm
C2 = 1.2  104 · mol/L
When open to air
Learning Check
What is the concentration of dissolved nitrogen

in a solution that is saturated in N 2 at 2.0 atm?
kH= 8.42×107 (M / atm)

• Cg=kHPg
• Cg= 8.42×107 (M / atm) × 2.0 atm
• Cg=1.7 ×10 6 M

Your Turn!
 How many grams of oxygen gas at 1.0 atm
will dissolve in 10.0 L of water at 25 oC if
Henry’s constant is 1.3 x 10-3 M atm-1 at this
temperature ?
Personal
A. 0.42 g use only !!!
B. 0.013 g
C. 0.042 g
D. 0.21 g
E. 2.4 g
Solubility of Polar vs. Nonpolar Gases
 Gas molecules with polar bonds are much more
soluble in water than nonpolar molecules like oxygen
and nitrogen
 CO2, SO2, NH3 >> O2, N2, Ar
 Form H-bonds with H2O

 Some gases have increased solubility because they
react with H2O to some extent
Ex. CO2(aq) + H2O H2CO3(aq) H+(aq) + HCO3–
(aq)
SO2(aq) + H2O H2SO3(aq) H+(aq) + HSO3–(aq)
NH3(aq) + H2O NH4+(aq) + HO–(aq)

Case Study
When you open a bottle

of seltzer, it fizzes. How
should you store it to
increase the time before
it goes flat?
Gases are more soluble at

low temperature and high
pressure. Cap it and cool it.

Concentration
 What units we use depends on situation
 Stoichiometric calculations
 Molarity mol of solute
M=
L of solution

 Units: mol/L
Problem: M varies with temperature
 Volume varies with temperature
 Solutions expand and contract when heated
and cooled
 If temperature independent concentration
is needed, must use other units
Temperature Insensitive
Concentration
1. Percent Concentrations
 Also called percent by mass or percent by
weight

percent by mass =
mass of solute
mass of solution
×100
 This is sometimes indicated %(w/w) where “w”

stands for weight
 The “(w/w)” is often omitted

Ex. Percent by Mass
What is the percent by mass of NaCl in a
solution consisting of 12.5 g of NaCl and 75.0
g water?
mass of solute
percent by mass =
mass of solution
×100
12. 5 g
wt NaCl = ×100
(12 . 5 + 75. 0 )g
wt NaCl =14. 3 NaCl

Learning Check
Seawater is typically 3.5% sea salt and has a density
of 1.03 g/mL. How many grams of sea salt would be
needed to prepare enough seawater solution to fill a
62.5 L aquarium?
What do we need to find?

 62.5 L  ? g sea salt
What do we know?
 3.5 g sea salt  100 g solution
 1.03 g soln  1.00 mL solution
 1000 mL  1.00 L
1000 mL 1. 03 g soln 3 . 5 g sea salt
62 .5 L × × ×
1L 1. 00 mL soln 100 g soln
= 2.2×103 g sea salt
More Temperature Insensitive
Concentration Units
Molality (m)
 Number of moles of solute per kilogram solvent
mol of solute
molality =m=
 Also Molal concentration
kg of solvent
 Independent of temperature
 m vs. M
 Similar when d = 1.00 g/mL
 Different when d >> 1.00 g/mL or
d << 1.00 g/mL
Ex. Concentration Calculation
If you prepare a solution by dissolving 25.38 g of I 2 in
500.0 g of water, what is the molality ( m) of the
solution?
 25.38 g  ? m

What do we know?
 253.8 g I2  1 mol I2
 m = mol solute/kg solvent
 500.0 g  0.5000 kg
Solve it 25 . 38 g I ×1 mol I 2 × 1
2
253 . 8 g I2 0 .5000 kg water
= 0.2000 mol I2/kg water = 0.2000 m
Ex. Concentration Calc’n. (cont)
What is the molarity (M) of this solution? The density
of this solution is 1.00 g/mL.
 25.38 g  ? M
What do we know?
 253.8 g I2  1 mol I2
 M = mol solute/L soln
 1.00 g soln  1 mL soln
Solve it
1 mol I 2 1 1. 00 g 1000 mL
25 . 38 g I2 × × × ×
253 . 8 g I2 525 . 38 g solnr 1. 00 mL 1 L
= 0.1903 mol I2/ L soln = 0.1903 M
Ex. M and m in CCl4
What is the molality (m) and molarity (M) of a solution
prepared by dissolving 25.38 g of I2 in 500.0 g of CCl4?
The density of this solution is 1.59 g/mL.
 25.38 g  ? m

What do we know?
 253.8 g I2  1 mol I2
 m = mol solute/kg solvent
 500.0 g soln  0.5000 kg soln
Solve it
1 mol I 2 1 1 . 00 g 1000 mL
25 . 38 g I2 × × × ×
253 . 8 g I2 500 . 0 g water 1. 00 mL 1 L
= 0.2000 mol I2/kg CCl4= 0.2000 m
Ex. M and m in CCl4 (cont)
What is the molarity (M) of this solution? The density
of this solution is 1.59 g/mL.
 25.38 g  ? M
What do we know?
 253.8 g I2  1 mol I2
 M = mol solute/L soln
 1.59 g soln  1 mL soln
 g of soln = g I2 + g CCl4 = 500.0 g + 25.38 g
Solve it 1 mol I 2 1 1 .59 g 1000 mL
25 . 38 g I2 × × × ×
253 . 8 g I2 525 . 38 g soln 1 . 00 mL 1 L
= 0.3030 mol I2/L soln = 0.3030 M
Converting between Concentrations
Calculate the molarity and the molality of a 40.0%
HBr solution. The density of this solution is 1.38
g/mL.
40. 0g HBr
40 . 0 HBr =wt% = ∗100
100 g solution

If we assume 100.0 g of solution, then 40.0 g of HBr.
m=
mol HBr
kg of H 2 O
mol HBr=
40 . 0g HBr
=0 . 494 mol HBr
80. 91 g HBr/ mol
If 100 g solution, then
mass H2O = 100.0 g soln – 40.0 g HBr = 60.0 g H2O
mol HBr 0 . 494 mol HBr
m= = =8 . 24 m
kg H 2 O 0 . 0600 kg H 2 O
Converting between Concentrations
(cont.)
Now Calculate Molarity of 40% HBr
mol HBr
M=
L solution

Vol Soln=
mass
=
100 g
density 1 .38 g /mL
= 72.46 mL
mol HBr = 0.494 mol

0 . 494 mol HBr 1000 mL
M= × = 6.82 M
72 . 46 mL solution 1L

Your Turn!
What is the molality of 50.0% (w/w) sodium
hydroxide solution?
A. 0.500 m
B. 1.25 m
C. 0.025 m

D. 25 m
E. 50 m
100.0 g soln = 50.0 g NaOH + 50.0 g water
1 mol NaOH 1 m 1000 g 1

50 . 0 g NaOH× × × ×
40 . 00 g NaOH mol/kg 1 kg 50 . 0 g water
= 25 m
MM(g/mol) H2O: 18.02; NaOH: 40.00

Your Turn!
 What is the molarity of the 50%(w/w) solution if its
density is 1.529 g/mL?
A. 19 M
B. 1.25 M

C. 1.9 M
D. 0.76 M

Your Turn! - Solution
1 mol NaOH g soln

50 g NaOH x x 1.529
40.0 g mL
1 1000 mL
x
100 g soln
x
L
= 19M
or
mmol 50 g H2 O 1.529 g
25 x x  19M
g soln 100 g soln mL

Other Temperature Insensitive
Concentration Units
 Mole Fraction
# mol A
χ A=
Total moles of all components
Personal
 Mole % use only !!!
mol %A= χ A∗100

Colligative Properties
 Physical properties of solutions
 Depend mostly on relative populations of
particles in mixtures
 Don’t depend on their chemical identities

Effects of Solute on Vapor Pressure of Solvents
 Solutes that can’t evaporate from solution are
called nonvolatile solutes
Fact: All solutions of nonvolatile solutes have
lower vapor pressures than their pure solvents

Raoult's Law
 Vapor pressure of solution, Psoln, equals
product of mole fraction of solvent, Xsolvent,
and its vapor pressure when pure, Psolvent
 Applies for dilute solutions
Personal
P = X use
P only !!!
solution solvent
∘
solvent
P solution = vapor pressure of the solution

X solvent = mole fraction of the solvent
P ∘solvent =vapor pressure of pure solvent
Alternate form of Raoult’s Law
 Plot of Psoln vs. Xsolvent
should be linear
∘
 Slope = P solvent
 Intercept = 0

 Change in vapor
pressure can be
expressed as
ΔP =change in P=( P∘solvent −P solution )
 Usually more interested in how solute’s mole fraction
changes the vapor pressure of solvent
∘
ΔP = X solute P solvent
Ex. Glycerin (using Raoult’s Law)
Glycerin, C3H8O3, is a nonvolatile nonelectrolyte with a
density of 1.26 g/mL at 25 °C. Calculate the change
in vapor pressure as 25 °C of a solution made by
adding 50.0 mL of glycerin to 500.0 mL of water.
The vapor pressure of pure water at 25 °C is 23.8
torr.
To solve use:
∘
ΔP = X solute P solvent
First we need Xsolute, so we need mole glycerin
and mole H2O.

Ex. Glycerin (cont.)
Mole glycerin
g 1 mol C3 H 8 O3
50 . 0 mL C3 H 8 O3 ×1 . 26 ×
mL 92. 1g C3 H 8 O 3
¿ 0 .684 mol C 3 H 8 O 3
Mole water

500 . 0 mL H 2 O×1 .00
Mole fraction glycerin
g
×
1 mol H2 O
mL 18 . 02 g H 2 O
=27 . 75 mol H 2 O
0 .684 mol −2
XC H O = =2 . 4 0 6×10
3 8 3
( 27 . 75+0 . 684 ) mol
∘
ΔP = X solute P solvent = ( 2. 4 0 6×10 )×23. 8 torr
−2
= 0.573 torr
Ex. Glycerin (cont.)
What is the final pressure?
 Can solve two ways:
∘ ∘
ΔP =P solvent −P solution P solution =P solvent − ΔP

 Or
P soln=23 .8 torr −0 .573 torr =23 . 2torr
27 . 75 mol
X H O= =0 . 9759
2
( 27 . 75+0 . 684 ) mol
∘
P solution= X solvent Psolvent
=( 0 .9759 )×23 .8 torr=23. 2 torr
Learning Check
The vapor pressure of 2-methylhexane is 37.986 torr at
15°C. What would be the pressure of the mixture of 78.0
g 2-methylhexane and 15 g naphthalene, which is nearly
non-volatile at this temperature?
Psolution = XsolventPosolvent

15 g
mole naphthalene= =0. 1 1 7 mol
naphthalene
128 .17 g/mol
C10H8 78 . 0 g
MM 128.17 mole 2-methylhexane= =0 .77 8 4 mol
100 . 2 g/mol
0 . 77 8 4 mol
X 2−methylhexane= =0. 8 6 9
2-methylhexane 0 . 77 8 4 mol + 0 . 11 7 mol
C7H16
MM 100.2 P=( 0 .8 6 9×37. 986 torr )
= 33.02 torr = 33 torr
Why Nonvolatile Solute Lowers
Vapor Pressure
 To evaporate, molecule must have enough
Kinetic Energy to escape surface—say 1%
 Only those molecules escape
 Set up equilibrium between liquid and vapor
 Add solute to solvent to get 20% (w/w) solution
 Now only 1% of 80% solvent can escape or 0.8%
of all molecules
 So vapor pressure  because fraction of
solvent molecules capable of leaving
solution 

Why Nonvolatile Solute Lowers Vapor
Pressure
A. Lots of solvent molecules in liquid phase
 Rate of evaporation and condensation high
B. Fewer solvent molecules in liquid
 Rate of evaporation lower

 At equilibrium, fewer molecules in gas phase
 Vapor pressure lower

Solutions That Contain Two or
More Volatile Components
 Now vapor contains molecules of both
components
 Partial pressure of each component A and B is
PersonalP =use
X P only !!!
given by Raoult’s Law
A
∘
A A
∘
P B =X BPB
 Total pressure of solution of components A and
B given by Dalton’s Law of Partial Pressures
∘ ∘
P total = P A +P B =X A P A+ X B P B
For Ideal, Two Component Solution
of Volatile Components
∘ ∘
P Total=P A+P B= X A P A + X B P B

∘
P A= X A P A
∘
P B =X BPB

Ex. Benzene and Toluene
 Consider a mixture of benzene, C6H6, and
toluene, C7H8, containing 1.0 mol benzene
and 2.0 mol toluene. At 20 °C, the vapor
pressures of the pure substances are:

P°benzene = 75 torr
P°toluene = 22 torr
 Assuming the mixture obeys Raoult’s law,
what is the total pressure above this
solution?

Ex. Benzene and Toluene (cont.)
1. Calculate mole fractions of A and B
1 .0 mol
X benzene = =0 . 33 benzene
(1 . 0+2 . 0 ) mol
2 . 0 mol
X toluene = =0 . 67 toluene
(1 . 0+2 . 0 ) mol
Personal
P =X ∗P
use only
=0 . 33×75 torr =25 torr
benzene benzene
!!!
2. Calculate partial pressures of A and B
∘
benzene
P toluene = X toluene∗P ∘toluene =0 . 67×22torr =15torr
3. Calculate total pressure
P total = Pbenzene + P toluene
¿( 25+15 )torr =40 torr
Learning Check
The vapor pressure of 2-methylheptane is
233.95 torr at 55°C. 3-ethylpentane has a
vapor pressure of 207.68 at the same
temperature. What would be the pressure of
the mixture of 78.0g 2-methylheptane and 15
g 3-ethylpentane?
2-methylheptane 3-ethylpentane
C8H18 C7H16
MM 114.23 g/mol MM 100.2 g/mol
Psolution = XAPoA + XBPoB

Learning Check
78. 0 g
mole 2-methylheptane= =0 . 68 28 mol
114 . 23 g/mol
15 g
mole 3-ethylpentane= =0 .1 4 97 mol
1 00 . 2 g/mol
0 . 68 2 83 mol
X 2-methylpentane= =0 . 8 2 7
(0 . 68 2 83 mol +0 .14 97 mol )
0 .1 4 97 mol
X 3-ethylpentane= =0 . 1 73
(0 . 68 283 mol +0 . 1 4 97 mol)
P=( 0 .8 2 7×233 . 95 torr ) + ( 0 .1 7 3×207 .68 torr )
P = 230 torr

Your Turn!
n-hexane and n-heptane are miscible in a large degree
and both volatile. If the vapor pressure of pure
hexane is 151.28 mm Hg, and heptane is 45.67 at
25º, which equation can be used to determine the
mole fraction of hexane in the mixture if the mixture’s

vapor pressure is 145.5 mm Hg?
A. X(151.28 mmHg) = 145.5 mmHg
B. X(151.28 mmHg) + (X)(45.67 mm Hg) = 145.5
mmHg
C. X(151.28 mmHg) + (1 – X)(45.67 mm Hg)
= 145.5 mm Hg
D. None of these

Solutes also Affect Freezing and
Boiling Points of Solutions
Facts:
 Freezing Point of solution always Lower
than pure solvent

 Boiling Point of solution always Higher
than pure solvent
Why?
 Consider the phase diagram of H2O
 Solid, liquid, gas phases in equilibrium
 Blue lines
 P vs. T
Pure Water
 Triple Point (TP)
 All 3 phases exist in 760
equilibrium
simultaneously

 Pure H2O
 Dashed lines at 760 torr
(1 atm) that intersect
solid/liquid and TFP TBP
TP
liquid/gas curves
 Give T for Freezing
Point (FP) and Boiling
Point (BP)
Solution—Effect of Solute
 Solute molecules stay
in solution only
 None in vapor
 None in solid
 Crystal structure prevents

from entering
 Liquid/vapor
  number solvent
molecules entering vapor
 Need higher T to get all
liquid to gas
 Line at higher T along
phase border (red)
Solution—Effect of Solute
 Triple point lower
and to left ()
 Solid/liquid
 Solid/liquid line to left

(red)
 Lower T all along
phase boundary
 Solute keeps solvent
in solution longer
 Must go to lower T to
form crystal
Freezing Point Depression and
Boiling Point Elevation
Solution
 Observe  BP and FP over pure solvent
 Presence of solute, depresses FP and elevates BP
 Both Tf and Tb depend on relative amounts of

solvent and solute
Colligative properties
 Boiling Point Elevation (Tb)
  in boiling point of solution vs. pure solvent
 Freezing Point Depression (Tf )
  in freezing point of solution vs. pure solvent

Freezing Point Depression (Tf)
Tf = iKf m
where
Tf = (Tfp  Tsoln)

m = concentration in Molality
Kf = molal freezing point depression constant
Units of °C/molal
Depend on solvent, see Table 13.3
i = number of particles per formula unit
= 1 for molecular compounds

Boiling Point Elevation (Tb)
Tb = iKb m
where
Tb = (Tsoln  Tbp)

m = concentration in Molality
Kb = molal boiling point elevation constant
Units of °C/m
Depend on solvent, see Table 13.3
i = number of particles per formula unit
= 1 for molecular compounds

Table 13.3 Kf and Kb

Ex. Freezing Point Depression
Estimate the freezing point of a permanent type of
antifreeze solution made up of 100.0 g ethylene
glycol, C2H6O2, (MM = 62.07) and 100.0 g H2O (MM
= 18.02).
1 mol C 2 H 6 O2
100 .0g C 2 H 6 O2 × = 1.611mol C2H6O2

62 . 07 g C2 H 6 O 2
mol solute 1 . 611 mol C 2 H 6 O 2
m= = = 16.11m C2H6O2
kg solvent 0 .100 kg water
Tf = Kfm = (1.86 °C/m) × 16.11m = 30.0 °C
Tf = (Tfp  Tsoln)
30.0 °C = 0.0 °C – Tsoln
= –30.0 °C
Tsoln = 0.0 °C – 30.0 °C
Your Turn!
 When 0.25 g of an unknown organic compound is
added to 25.0 g of cyclohexane, the freezing point
of cyclohexane is lowered by 1.6 oC. Kf for the
solvent is 20.2 oC m-1. Determine the molar mass of
the unknown.

A. 505 g/mol
B. 32 g/mol Tf  K f m
C. 315 g/mol  0.250 g 
D. 126 g/mol o
C  MW 
o
1.6 C=20.2 x  
m 0.025 kg
MW  126 g/mol
Ex. Boiling Point Elevation
A 2.00 g sample of a large biomolecule was dissolved
in 15.0 g of CCl4. The boiling point of this solution
was determined to be 77.85 °C. Calculate the molar
mass of the biomolecule. For CCl4, the Kb = 5.07
°C/m and BPCCl4 = 76.50 °C.

ΔT b =K b m m=
ΔT b ( 77 .85−76 .50 ) ∘ C
Kb
= ∘
5 .07 C /m
=0. 26 8 4m
mol solute mol solute=0 . 26 8 4m×0 . 0150 kg CCl4
m=
kg solvent −3
¿ 4 . 0 2 6×10 mol
2. 00 g biomoleucle
MM biomolecule = −3
=497 g /mol
4 . 0 2 6×10 mole
Learning Check
According to the Sierra™ Antifreeze literature,
the freezing point of a 40/60 solution of Sierra
antifreeze and water is – 4 °F. What is the
molality of the solution?
Personal use
ΔT only
=m×K !!!
TF = 1.8 TC + 32
– 4°F = 1.8 X + 32
solution
∘
fp
∘ 1. 86 C
(0−(−20 .) C= X ×
X = – 20. °C m
T = Tfp – Tsoln
X = 11m

Learning Check
In the previous sample of a Sierra™ antifreeze
mixture, 100 mL is known to contain 42 g of the
antifreeze and 60. g of water. What is the molar
mass of the compound found in this antifreeze if it
has a freezing point of – 4°F?
Personal moluse
From before:
X = 11 m
m=
solute only !!!
kg solvent
mol solute=11 m×0 . 060 kg solvent
= 0.66 mol solute
42 g solute MM solute
MM=
0. 66 mol solute = 64 g/mol
Learning Check
In the previous sample of a Sierra™ antifreeze
mixture, the freezing point is – 4°F. What will
be its boiling point? ΔT =m×K fp fp
From before:
Personal use
ΔT only
– 4°F = – 20. °C
=
K
=m
!!! ΔT bp=m×K bp
Freezing Point fp
ΔT Boiling Point K bp
(0 ∘C−(−20∘C )) 1. 86∘ C/ m
=
T boil−100∘C 0. 51 ∘C/ m
Tboiling =105 °C
Your Turn!
Beer is known to be around a 5% ethanol
(C2H5OH) solution with a density of 1.05 g/mL.
What is its expected boiling point? (K b=0.51°/m)

A. 100ºC
B. 101ºC
C. 102ºC
D. 103ºC
E. Not enough information given
MM: H2O=18.0153; C2H5OH=46.069
Membranes and Permeability
Membranes
 Separators
 Ex. Cell walls
 Keep mixtures organized and
separated

Permeability
 Ability to pass substances
through membrane
Semipermeable
 Some substances pass, others
don’t
 Membranes are semipermeable
 Selective
Membranes and Permeability
 Degree of permeability depends on type of
membrane
 Some pass water only
 Some pass water and small ions only
 Membranes separating two solutions of different

concentration
 Two similar phenomena occur
 Depends on membrane
Dialysis
 When semipermeable membrane lets both H2O and
small solute particles through
 Membrane called dialyzing membrane
 Keeps out large molecules such as proteins
Osmosis
Osmotic Membrane
 Semipermeable membrane that lets only solvent
molecules through
Osmosis
 Net shift of solvent molecules (usually water)
through an osmotic membrane
 Direction of flow in osmosis,
 Solvent flows from dilute to more concentrated side
 Flow of solvent molecules across osmotic membrane
  concentration of solute on dilute side
  concentration of solute on more concentrated side

Osmosis and Osmotic Pressure

A. Initially, Soln B separated from pure water, A, by
osmotic membrane. No osmosis occurred yet
B. After a while, volume of fluid in tube higher. Osmosis
has occurred.
C. Need back pressure to prevent osmosis = osmotic
pressure.
Osmotic Pressure
 Exact back pressure needed to prevent osmotic
flow when one liquid is pure solvent.
Why does osmosis eventually stop?
 Extra weight of solvent as rises in column

generates this opposing pressure
 When enough solvent transfers to solution so that
when osmotic pressure is reached, flow stops
 If osmotic pressure is exceeded, then reverse
process occurs—solvent leaves solution
 Reverse osmosis—used to purify sea water

Equation for Osmotic Pressure
 Assumes dilute solutions
 = iMRT
  = osmotic pressure
 i = number of ions per formula unit

= 1 for molecules
 M = molarity of solution
 Molality, m, would be better, but M simplifies
 Especially for dilute solutions, where m  M
 T = Kelvin Temperature
 R = Ideal Gas constant
= 0.082057 L·atm·mol1K1
Van’t Hoff Equation
 Since
mol n
M= =
L V
 Substitute into osmotic pressure equation
 Get van’t Hoff Equation for osmotic
pressure
V = inRT
 V = volume in L
 n = moles
 Identical to Ideal Gas Law
 But with P =  (osmotic pressure)
Osmometer
 Instrument to measure osmotic pressure
 Very important in solutions used for
biological samples
Isotonic solution
 Same salt concentration as cells
 Same osmotic pressure as cells

Hypertonic solution
 Higher salt concentration than cells
 Higher osmotic pressure than cells
 Will cause cells to shrink and dehydrate
Hypotonic solution
 Lower salt concentration than cells
 Lower osmotic pressure than cells
 Will cause cells to swell and burst
Ex. Osmotic Pressure
Eye drops must be at the same osmotic pressure
as the human eye to prevent water from moving
into or out of the eye. A commercial eye drop
solution is 0.327 M in electrolyte particles. What is
the osmotic pressure in the human eye at 25 °C?
Personal
 = MRT T(K)use
= 25°C +only
273.15 !!!
L⋅atm
Π =0 .327 M ∗0 .08206 ∗298 K =8 . 00 atm
K⋅mol

Ex.2 Using  to determine MM
The osmotic pressure of an aqueous solution of certain
protein was measured to determine its molar mass. The
solution contained 3.50 mg of protein in sufficient H2O to
form 5.00 mL of solution. The measured osmotic pressure
of this solution was 1.54 torr at 25 °C. Calculate the molar
Personal
( use only !!!
mass of the protein.
M=
Π )
=
1. 54 torr
1 atm
760torr
=8. 28×10
−5 mol
RT
( 0 . 08206
L⋅atm
K⋅mol
298 K ) L
mol =M ∗L=( 8 . 28×10−5 M )∗5. 00×10−3 L=4. 14×10−7 mol
−3
g 3. 50×10 g 3
MM = = =8. 45×10 g / mol
mol 4 .14×10 mol
−7

Learning Check: Osmosis
A solution of D5W, 5% dextrose (C6H1206) in
water is placed into the osmometer shown at
right. It has a density of 1.0 g/mL. The
surroundings are filled with distilled water.
What is the expected osmotic pressure at
Personal
25°C?
Π =iMRT use only !!! i = 1 as dextrose is molecular
5g C6 H 12 O6 1 . 0g soln mol C 6 H 12 O6 1000mL
× × × =M
100g solution mL soln 180 .16g L
0. 277 mol 0. 082057 L⋅atm
Π= × ×298K
L mol⋅K
 = 7 atm
Learning Check
For a typical blood plasma, the osmotic pressure at
body temperature (37°C) is 5409 mm Hg. If the
dominant solute is serum protein, what is the
concentration of serum protein?
Π =MR T
5409 mm Hg 1atm
× =Π
760 mm Hg
? mol 0. 082057 L⋅atm
7 .117 atm= × ×3 10 .1 5K
L mol⋅K
M = 0.280 M
Your Turn!
Suppose that your tap water has 250 ppb
(ppb = 1/1,000,000,000 or 1×10 –9) of
dissolved H2S , and that its density is about
1.0 g/mL. What is its osmotic pressure at

25°C?
A. 0.00058 atm
B. 0.064 atm
C. 0.059 atm
D. 0.18 atm
MM: H2S =34.076
Colligative Properties of Electrolyte
Solutions Differ
 Kf (H2O) = 1.86 °C/m
 Expect 1.00 m solution of NaCl to freeze at
1.86 °C
 Actual freezing point = 3.37 °C

 ~ twice expected T
Why?
 Colligative properties depend on
concentration (number) of particles
 1 NaCl dissociates to form 2 particles
NaCl  Na+(aq) + Cl(aq)
Colligative Properties of Electrolyte
Solutions Depend on Number Of Ions
 Actual concentration of ions = 2.00 m
(Started with 1.00 m NaCl)
 Now use this to calculate T
 Tf = 1.86 °C/m  2.00 m = 3.72 °C
Or
 Tfinal = Tinitial – Tf = 0.00 – 3.72 °C
= – 3.72 °C
 Not exactly = to actual Tf = 3.37 °C
 This method for ions gives rough estimate if
you assume that all ions dissociate 100%.
Why isn’t this Exact for Electrolytes?
 Assumes 100% dissociation of ions
 Electrolytes don’t dissociate 100%, especially in
concentrated solutions
 Some ions exist in ion pairs
 Closely associated pairs of oppositely charged ions that

behave as a single particle in solution
 So, fewer particles than predicted
 Result: FPD and BPE not as great as expected
 As you go to more dilute solutions, electrolytes
more fully dissociated and observe FP and BP
closer to calculated value.
 Model works better at dilute concentrations

van’t Hoff Factor = i
 Scales solute molality to correct number of
particles
 Measure of dissociation of electrolytes
 van’t Hoff factor is equivalent to percent

ionization
 In general, it varies with concentration (see
Table 13.4, page 622)
( ΔT f ) measured
i=
( ΔT f )calcd as nonelectrolyte
Table 13.4 van’t Hoff Factors vs.
Concentration

Note:
1. as concentration , iobserved  iexpected
2. MgSO4 much less dissociated than NaCl or KCl
Why Does MgSO4 Dissociate Less
Than NaCl or KCl?
 MgSO4  Mg2+ (aq) + SO42 (aq)
 2+/2 ions rather than 1+/1 ions
 Larger charge means greater attractive forces

between oppositely charged ions
So for AlPO4 would we expect more or less
dissociation than MgSO4?
 AlPO4  Al3+ (aq) + PO43 (aq)
 Larger charges (3+/3) expect greater
attractions and less dissociation
Nonelectrolytes
 Some molecular solutes produce weaker
colligative effects than predicted by their molal
concentrations
 Evidence of solute molecule clustering or

associating
O O H O
2 C6H5 C C6H5 C C C6H5
O H O H O
 Result: only ½ number of particles expected

based on molality of solution, so Tf only ½
what expected
Nonelectrolytes
O O H O
2 C6H5 C C6H5 C C C6H5
O H O H O
 or

 Result: MM double what is expected
 [particles] = ½ what is expected and
 Tf only ½ what expected
 So size of solute particles is important
 Common with organic acids and alcohols

Learning Check
In preparing pasta, 2 L of water at 25°C are combined
with about 15 g salt (NaCl, MM= 58.44g/mol) and the
solution brought to a boil. What is the expected boiling
point of the water?
ΔT=imKbp

mass of water = volume × density = 2000 mL × 1.0 g/mL
= 2000g water = 2 kg
mol NaCl = 15 g / 58.44 g/mol = 0.25667 mol
mNaCl = 0.25667 mol / 2kg = 0.123 m
∘ 2 ion 0 .1 23 m 0 .51 ∘
C
T −100 C = × ×
mol 1 m
T = 100.1 °C
Case Study
Suppose you run out of salt. What mass of
sugar (C12H22O11, MM=342.30 g/mol) added to
2 L of water would raise the temperature of
water by 0.10 °C? ΔT=imKbp

∘
∘ 1 ion 0 .51 C
0.10 C = ×X × X = 0.196 m
mol m
mass of water = volume × density = 2000 mL × 1.0 g/mL
= 2000g water = 2 kg 0.196 m = X / 2kg
X = 0.39215 mol
0.39215 mol = mass sucrose / 342.30 g/mol
mass of sucrose =130 g
Colligative Properties Summary
Colligative properties depend on number
of particles
 i = mapp/mmolecular
 Raoult’s Law

Freezing Point Depression

 Boiling Point Elevation
 Osmotic Pressure
Must look at solute and see if molecular
or ionic
 If molecular, i = 1
 If ionic, must include i > 1 in equations
Colligative Properties
 Raoult’s Law
∘
P solution = X solvent P solvent
 Freezing Point Depression

 Tf = iKf m
 Boiling Point Elevation
 Tb = iKb m
 Osmotic Pressure
  = iMRT

Brdy 6ed Ch13 MixturesAtTheMolecularLevel

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Chapter 13:

Mixtures at the Molecular

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

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Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

• We see that pressure has no infuence on the solubility of liquids

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 Attractive forces between solute and

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Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 23

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Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 24

Personal use only !!!

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 25

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Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 26

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Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 27

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Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 28

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Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 29

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 30

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 31

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Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 32

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Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 33

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Hsoln = 632 kJ mol–1

Personal use only !!! – 619 kJ mol–1

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 35

Hsoln = 728 kJ mol–1

Personal use only !!! – 741 kJ mol–1

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E 36

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Personal use only !!!

Personal use only !!!

 Step 1 + Step 2 = –Step 3