Point function :

Those quantities which depends upon the end states of the system undergoing a process (i.e. change of state) are known as point functions. These quantities are exact differential. These quantities are properties of a system. Example : Pressure, volume, temperature, internal energy etc.

Path function :

dp = p2 p1 an exact differential

Those quantities which depends upon the path followed by the system undergoing a process (i.e. change of state) are known as path functions. These quantities are inexact differential. These quantities are not properties of a system. Example : Heat and work etc.

dQ = Q 1-2 an inexact differential

Heat :
Heat is a form of energy which is transferred from one body to another body or between system and surroundings from higher temperature to lower temperature by virtue of temperature difference between two bodies. It is denoted by Q. Its unit is Joule or kilo Joule (represented by K or KJ). Transfer of heat to the system is known as heat addition and transfer of heat from the system is known as heat rejection. It is an extensive property. Heat is a path function and inexact differential.

Sign convention :
Heat transferred (or supplied) to the system is taken as positive (+ ve). Heat transferred (or rejected) from the system is taken as negative(ve).

Work :
Work is done by or on the system if the sole effect on the things external to the system could be equivalent to raising or lowering a weight in the surroundings. It is denoted by W and its unit is N-m in S I system.

Consider a storage battery as a system and a motor, frictionless pulley and weight as surroundings. Electrical energy is supplied to the motor which utilizes this energy to raise a weight through a distance z.

Sign convention :
Work done by the system is positive (+ ve). Work done on the system is negative (ve).

Similarity between heat and work :

(i) Both heat and work are energy in transit and these are never contained in a system. (ii) Both heat and work transfer are boundary phenomenon. (iii) Both heat and work are path functions and not the properties of the system. Both are inexact differential.

Difference between heat and work :

(i) Heat transfer takes place when there is temperature difference between system and surroundings. While work transfer takes place without temperature difference. (ii) In case of constant volume process, there is no work transfer while heat can be transferred.

Work done in moving a boundary of a closed system in a quasi-static process :

Consider a certain amount of gas contained in a piston-cylinder arrangement. The pressure exerted by the gas is being balanced by the weights on the piston so the system is in equilibrium. If we remove a very small amount of weight, piston will move through a small distance dl. Let p be the pressure exerted by the gas and A be cross-sectional area of the piston.

Force exerted on the piston = p.A Consider the process to be quasi-static, work done by the system dW = p.A.dl dW = p.dV For a process 1-2 W12 =

pdV
1

(i)

Equation (i) is valid for quasi-static and reversible process only. Work obtained from equation (i) is represented by area under the process curve on p-V diagram. Since volume increases from state 1 to 2 so area under the curve represents work done by the system (i.e. positive).

Limitations of pdV work :

1

(a) System is closed. (b) Process is quasi-static and reversible. (c) Effects due to gravity, magnetism and electricity are neglected.

Free expansion :
Consider a gas separated from vacuum by a partition. If partition is removed the gas rushes to fill the entire volume. The expansion of a gas against vacuum is called free expansion. If work associated with the removal of partition is neglected and consider gas and vacuum together as system then there is no work transfer since no work crosses the system boundary i.e.

pdV 0 while dW = 0
1 1

As pressure and volume of gas change during the process so work exists but it is an internal work.

pdV
1

Specific heat :
Specific heat of any substance is defined as the amount of heat required to raise the temperature of 1 kg of substance by 10C. Mathematically, Q = m C t Q C= mt Where Q : heat transfer (kJ) m : mass of substance (kg) t : rise in temperature (0C or K) Unit of specific heat kJ/kg.0C or kJ/kg. K.

Specific heat at constant volume :

It is the amount of heat required to raise the temperature of unit mass of gas by one degree (10C) at constant volume. It is denoted by Cv and its unit is kJ/kg. K.

Specific heat at constant pressure :

It is the amount of heat required to raise the temperature of unit mass of gas by one degree (10C) at constant pressure. It is denoted by Cp and its unit is kJ/kg. K. Adiabatic index : Ratio of specific heat at constant pressure to specific heat at constant volume is known as adiabatic index. It is denoted by (gamma). Cp = CV Q Cp > Cv (always) >1

 = 1.67 for mono-atomic gas = 1.40 for di-atomic gas = 1.33 for poly-atomic gas.

First law of Thermodynamic

(i) For a closed system undergoing a cycle
Algebraic sum of work transfer is proportional to algebraic sum of heat transfer i.e.

( W ) ( W )

cycle

( Q)

cycle

cycle

=J

( Q)

cycle

.(i)

where J : Joules equivalent or Mechanical equivalent of heat. J = 1.0 N-m / J (in S I system) J = 4.187 kJ / kcal (in M K S system) Equation (i) can also be represented as dW = J dQ

..(ii)

Cyclic integration for closed path. Equation (i) & (ii) represents first law of thermodynamics for a closed system undergoing a cycle.

(ii) For a closed system undergoing a change of state or process

If a system undergoes a change of state during which both heat transfer and work transfer are involved, the net energy transfer will be stored within system. Initial state P V Q amount of heat transferred or supplied to the system. W amount of work transferred from the system or work done by the system (Q W) amount of net energy transfer that will be stored in the system, known as energy of the system. It is represented by E. Q W = E

Final state

Q = E + W Q, W & E are in same unit (in Joule).

Energy, a property of the system :

Consider a system which changes its state from state 1 to state 2 by following path A and returns from state 2 to state 1 by following path B. Path A and path B together form a cycle. Initial state P V I- law for path A, I- law for path B, QA = W A + E A QB = WB + EB ..(i) .(ii)

Final state

Path A and path B together form a cycle so I-law for cycle, ( W ) cycle = ( Q ) cycle W A + W B = QA + QB QB + W B = QA W A (QB WB) = (QA WA) EB = EA

...(iii)

If system returns from state 2 to state 1 by following path C instead of path B. I- law for path C, QC = WC + EC ..(iv) Path A and path C together form a cycle so I-law for cycle, ( W ) cycle = ( Q ) cycle W A + W C = QA + QC QC + W C = QA W A (QC WC) = (QA WA) EC = EA From equation (iii) & (v), EB = EC

.(v)

 change in energy between two states of a system is same, whatever path the system will follow in undergoing that change of state. change in energy is independent of path followed by the system and depends on end states. Hence energy of a system is point function and property of the system. Energy E is an extensive property. E Specific energy e = (J / kg) is an intensive property. m Energy of a system includes, (a) Internal energy due to molecular motion and position (i.e. U) (b) External kinetic energy (i.e. KE) (c) External potential energy (i.e. PE) (d) Chemical energy (e) Electrical energy (d) Magnetic energy Neglecting all forms of energy except internal energy U, kinetic energy KE and potential energy PE, therefore KE2 +4 PE 3 { + 14 E= U
micro macro

In the absence of motion and gravity, KE = 0 & PE = 0 So, E=U I-law becomes, Q = U + W where U includes only energy due to molecular motion and position. I-law in differential form, dQ = dE + dW Internal energy U is an extensive property. U Specific internal energy u = (J / kg) is an intensive property. m Other forms of I-law of thermodynamics neglecting other works except p dV work dQ = dU + pdV or Q = U + pdV If Q, U & V are taken on unit mass basis, then dq = du + pdv or q = u + pdv Note : For an ideal gas internal energy is a function of temperature only. U = f (T) As there is no intermolecular force of attraction and repulsion.