Intensive Revision Program

of
Physical Chemistry

By : Brijesh Jindal Sir

KEY CONCEPTS
SOME BASIC DEFINITATIONS
System : the macroscopic part of the universe under study is called a system.
Surroundings : the rest of the universe outside the system is called surroundings.
Boundary : The actual or imaginary surface that separates the system from the surroundings is called
the boundary.
TYPES OF SYSTEMS
Isolated system : A system is said to be isolated if it cannot exchange matter and energy with the
surroundings. Example : coffee in a thermos flask.
Closed system : A system is said to be closed if it can exchange energy but not matter. Example :
Coffee in a closed stainless steel flask.
Open system : A system is said to be open if it can exchange matter. Example : A thermos flask or a
steel flask if not closed.

PROPERTIES OF SYSTEM
Extensive Properties Intensive Properties
Volume Molar volume
Number of moles Density
Mass Refractive index
Free Energy (G) Surface tension
Entropy (S) Viscosity
Enthalpy (H) Free energy per mole
Internal energy (E & U) Specific heat
Heat capacity Pressure
Temperature
Boiling point, freezing point etc

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 REVERSIBLE AND IRREVERSIBLE PROCESS
A process which is carried out so slowly that the system and the surroundings are always in equilibrium
is known as a Reversible Process (quasi-static). If this condition does not hold good, the process is
said to be, Irreversible.
In a reversible process the driving force is infinitesimally larger than the opposing force.
A reversible process in very slow and takes infinite time. Where as an irreversible process completes
in finite time.

WORK
Two types of work normally come across in chemistry. These are Electrical Work and
PV-work (pressure volume work)
In thermodynamics we mainly discuss PV-work
V2

WPV = –  Pext dV
V1

But later on we will discuss electrical work also Welectric = VIt

IUPAC convention for work :
* Work done by system is expressed with –ive sign
* Work done on system is expressed with +ive sign
HEAT
Heat is defined as the energy that flow into or out of a system because of a difference in temperature
between the thermodynamic system and its surrounding.
According to IUPAC convention heat given by system is expressed with -ive sign heat given to system
is expressed with +ive sign.
* qV = nCvdT
* qp = nCpdT
* Cp,m – Cv,m = R
* Cv & Cp depend on tempeture

INTERNAL ENERGY (E & U)

Every system having some quantity of matter is associated with a definite amount of energy, called
internal energy.
U = UKinetics + UPotential + UElectronic + Unuclear + .....

U is a state function & is an extensive property.

U = Ufinal – Uinitial
* For a given system
U = f (T, V)

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  U   U 
dU =   . dT +   dV
 T  v  V T

ZEROTH LAW OF THERMODYNAMICS

Two systems in thermal equilibrium with a third system are also in thermal equilibrium with each other.

FIRST LAW OF THERMODYNAMICS

"Total energy of universe remain constant." It is law of conservation of energy.
U = q + w,

ENTHALPY
Chemical reactions are generally carried out at constant pressure (atmospheric pressure) so it has
been found useful to define a new state function Enthalpy (H) as :
H = U + PV
H = U + (PV)
at constant pressure
H = U + P V
combining with first law.
H = qp
Hence transfer of heat at constant volume brings about a change in the internal energy of the system
whereas that at constant pressure brings about a change in the enthalpy of the system.

* For a given system

H = f (T, P)

 H   H 
dH =   . dT +   dP
 T  P  P  T

RELATIONSHIP BETWEEN H & U

The difference between H & U becomes significant only when gases are involved (insignificant in
solids and liquids)
H = U + (PV)
If substance is not undergoing chemical reaction or phase change.
H = U + nRT
In case of chemical reaction
H = U + ng)RT

CALCULATION OF WORK DONE IN VARIOUS PROCESS

1. Isothermal process

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 Since dT = 0  dU = 0 for an ideal gas
from Ist law q = – w
If process is reversible
V2
W = – nRT ln V
1

If process is irreversible

 nRT nRT 
W = – Pext  P  P 
 2 1 

In case of free expansion pext = 0

W=0
2. Isobaric process
W = – Pext (V2 – V1)
& H = qp

3. Isochoric process
Since dV = 0  W=0
from 1st law U = q

4. Adiabatic process :
q=0
P2 V2  P1V1
W = nCv (T2 – T1) =
 1
for reversible adiabatic process PV = constant.

5. Cyclic process
work done = Area enclose in PV-diagram P W
For clockwise it is –ive
For anti-clockwise it is +ive V

SECOND LAW OF THERMODYNAMICS

(i) No cyclic engine is possible which take heat from one single source and in a cycle completely convert
it into work without producing any change in surrounding.

(ii) In an irreversible process entropy of universe increases but it remains constant in a reversible process.
Ssyt + Ssurr = 0 for rev. process
Ssyt + Ssurr > 0 for irrev. process
Ssyt + Ssurr  0 ( In general )

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 PHYSICAL SIGNIFICANCE OF ENTROPY
One can think entropy as a measure of the degree of randomness or disorder in a system. The greater
the disorder, in a system, the higher is the entropy.

CALCULATION OF ENTROPY CHANGE

General Expression
T2 V2 T2 P1
S = nCV ln T + nR ln V or nCp ln T + nR ln P
1 1 1 2

Reversible & irreversible isothermal expansion and contraction of an ideal gas

U = 0; H = 0
V2
S = nR ln V
1

Isobaric heating or cooling :

U = CV T
H = CP T = qP

 T2 
S = nCP ln  T 
 1
Isochoric heating or cooling :
U = CV T = qV
H = CP T

 T2 
S = nCV ln  
 T1 
Adiabatic process :
U = CV T
H = CP T
T2 V2
S = nCV ln T + nR ln V for irreversible process
1 1

S = 0 for reversible adiabatic compression and expansion.

THIRD LAW OF THERMODYNAMICS

“At absolute zero, the entropy of a perfectly crystalline substance is taken as zero”, which means that
at absolute zero every crystalline solid is in a state of perfect order a n d its entropy should be
zero.
By virtue of the third law, the absolute value of entropy (unlike absolute value of enthalpy) for any pure
substance can be calculated at room temperature.

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 T
q rev
ST – S0K = 
0 T

since S0K = 0
T
q rev
ST = 
0 T

GIBBS FREE ENERGY (G) AND SPONTANEITY:

A new thermodynamic state function G , the Gibbs free energy is defined as :
G = H – TS
at constant temperature and pressure
G = H – T S
If G)T,P < 0 process is irreversible (spontaneous)
G)T,P = 0 process is reversible
G)T,P > 0 process is impossible (non spontaneous)
The use of Gibbs free energy has the advantage that it refers to the system only (and not surroundings).
To summaries, the spontaneity of a chemical reaction is decided by two factors taken together:
(i) the enthalpy factor and (ii) the entropy factor.
The equation G = H – T S takes both the factors into consideration.

(Hr
(
T,P (S r (
T,P (Gr
(
T,P Remarks
– ve + ve Always – ve Reaction is spontaneous

+ ve – ve Always + ve Reaction non spontaneous

At low temperature, G = + ve Non spontaneous

+ ve + ve
At high temperature, G = – ve Spontaneous

At low temperature, – ve Spontaneous

– ve – ve
At high temperature, +ve Non spontaneous

Variation of Gibb's function (G) with temperature and pressure :

dG = VdP – SdT
Also
–(dGsystem)T,P = (Wnon–PV) system
Non–PV work done by the system = decrease in gibbs free energy

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 EXERCISE

Only one correct :

Q.1 Out of boiling point (I), entropy (II), pH (III) and density (IV), Intensive properties are:
(A) I, II (B) I,II, III (C) I, III, IV (D) All of these

Q.2 Consider the reaction at 300 K

H2 (g) + Cl2 (g)  2HCl (g) H = – 185 kJ/mol
Calculate U if 3 mole of H2 completely react with 3 mole of Cl2 to form HCl.
(A) 0 (B) – 185 kJ (C) 555 kJ (D) None of these

Q.3 Ethyl chloride (C2H5Cl), is prepared by reaction of ethylene with hydrogen chloride:
C2H4(g) + HCl (g)  C2H5Cl (g) H = – 72.3 kJ/mol
What is the value of U (in kJ), if 70 g of ethylene and 73 g of HCl are allowed to react at 300 K.
(A) – 69.8 (B) –180.75 (C) –174.5 (D) –139.6

Q.4 What is U for the process described by figure. Heat supplied during the process q = 100 kJ.

(A) + 50 kJ (B) – 50 kJ (C) –150 kJ (D) + 150 kJ

Q.5 One mole of ideal gas is allowed to expand reversibly and adiabatically from a temperature of 27°C.
If the work done by the gas in the process is 3 kJ, the final temperature will be equal to (CV=20 J/K
mol)
(A) 100 K (B) 450 K (C) 150 K (D) 400 K

Q.6 What is the change in internal energy when a gas contracts from 377 ml to 177 ml under a constant
pressure of 1520 torr, while at the same time being cooled by removing 124 J heat?
[Take : (1 L atm) = 100 J ]
(A) –24 J (B) – 84 J (C) – 164 J (D) –248 J

Q.7 The heat capacity of liquid water is 75.6 J / mol.K, while the enthalpy of fusion of ice is 6.0 kJ/mol.
What is the smallest number of ice cubes at 0°C, each containing 9.0 g of water, needed to cool 500
g of liquid water from 20°C to 0°C?
(A) 1 (B) 7 (C) 14 (D) None of these

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 Q.8 An ideal gas is taken around the cycle ABCDA as shown in figure. The net work done during the cycle
is equal to :
P2 B D
P
P1
C
V1 V2
V
(A) zero (B) positive (C) negative (D) we cannot predict

Q.9 Molar heat capacity of water in equilibrium with ice at constant pressure is
(A) zero (B) 
(C) 40.45 kJ K mol
–1 –1
(D) 75.48 JK–1 mol–1

Q.10 A cyclic process ABCD is shown in PV diagram for an ideal gas. Which of the
following diagram represents the same process?

(A) (B)

(C) (D)

Q.11 A diatomic ideal gas initially at 273 K is given 100 cal heat due to which system did 209 J work.
Molar heat capacity (Cm) of gas for the process is :
3 5 5
(A) R (B) R (C) R (D) 5 R
2 2 4

Q.12 One mole of an ideal monoatomic gas expanded irreversibly in two stage expansion.
State-1 (8.0 bar, 4.0 litre, 300 K)
State-2 (2.0 bar, 16 litre, 300 K)
State-3 (1.0 bar, 32 litre, 300 K)
Total heat absorbed by the gas in the process is :
(A) 116 J (B) 40 J (C) 4000 J (D) None of these

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 Q.13 For an ideal monoatomic gas during any process T = kV, find out the molar heat capacity of the gas
during the process. (Assume vibrational degree of freedom to be active)
5 7
(A) R (B) 3R (C) (D) 4 R
2 2

5
Q.14 A gas (Cv,m = R) behaving ideally was allowed to expand reversibly and adiabatically from 1 litre to
2
32 litre. It's initial temperature was 327°C. The molar enthalpy change (in J/mole) for the process is
(A) –1125 R (B) – 575 R (C) –1575 R (D) None of these

Q.15 What is the net work done (in calories) by 1 mole of monoatomic ideal gas in a process described by
1, 2, 3, 4 in given V–T graph.

Use : R = 2cal / mole K

ln 2 = 0.7
(A) – 600 cal (B) – 660 cal (C) + 660 cal (D) + 600 cal

5
Q.16 Two moles of an ideal gas (CV = R) was compressed adiabatically against constant pressure of 2
2
atm. Which was initially at 350 K and 1 atm pressure. The work involve in the process is equal to
(A) 250 R (B) 300 R (C) 400 R (D) 500 R

Q.17 Two rigid adiabatic vessels A and B which initially, contain two gases at different temperatures are
connected by pipe line with valve of negligible volume. The vessel 'A' contain 2 moles Ne gas
 5 
 C p,m  R  at 300 K, vessel 'B' contain 3 moles of SO2 gas (Cp,m = 4 R) at 400 K.
 2 
The volume of A & B vessel is 4 and 6 litre respectively.
The final total pressure (in atm) when valve is opened and 12 Kcal heat supplied through it to vessels.
[Use : R = 2 cal / mol. K and R = 0.08 L . atm / mol K as per desire]
B
A

Ne SO2

(A) 3.5 atm (B) 7 atm (C) 35 atm (D) 70 atm

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 Q.18 An insulated container of gas has two chambers separated by an insulating partition. One of the chambers
has volume V1 and contains ideal gas at pressure P1 and temperature T1. The other chamber has
volume V2 and contains ideal gas at pressure P2 and temperature T2. If the partition is removed
without doing any work on the gas, the final equilibrium temperature of the gas in the container will be
T1T2 (P1V1  P2 V2 ) P1V1T1  P2 V2 T2
(A) P V T  P V T (B) P1V1  P2 V2
1 1 2 2 2 1

P1V1T2  P2 V2T1 T1T2 (P1V1  P2 V2 )

(C) P1V1  P2 V2 (D) P V T  P V T
1 1 1 2 2 2

Q.19 The maximum efficiency of a heat engine operating between 100°C and 25°C is
(A) 20.11% (B) 22.2% (C) 25.17% (D) None

Q.20 A heat engine operating between 227°C and 27°C absorbs 2 Kcal of heat from the 227°C reservoir
reversibly per cycle. The amount of work done in one cycle is
(A) 0.4 Kcal (B) 0.8 Kcal (C) 4 Kcal (D) 8 Kcal

Q.21 A reversible heat engine A (based on carnot cycle) absorbs heat from a reservoir at 1000K and rejects
heat to a reservoir at T2. A second reversible engine B absorbs, the same amount of heat as rejected
by the engine A, from the reservoir at T2 and rejects energy to a reservoir at 360K.
If the efficiencies of engines A and B are the same then the temperature T2 is
(A) 680 K (B) 640 K (C) 600 K (D) None

Q.22 For the reaction at 300 K

A(g) + B(g)  C (g)
E = –3.0 kcal ; S = – 10.0 cal/K
value of G is
(A) –600 cal (B) –6600 cal (C) –6000 cal (D) None

Q.23 The entropy change when two moles of ideal monoatomic gas is heated from 200 to 300°C reversibly
and isochorically
3  300  5  573   573  3  573 
(A) R ln   (B) R ln   (C) 3R ln   (D) R ln 
2  200  2  273   473  2  473 

Q.24 What is the free energy change G) when 1.0 mole of water at 100°C and 1 atm pressure is converted
into steam at 100°C and 1 atm pressure?
(A) 80 cal (B) 540 cal (C) 620 cal (D) zero

Q.25 What is the free energy change G) when 1.0 mole of water at 100°C and 1 atm pressure is converted
into steam at 100°C and 2 atm pressure?
(A) zero cal (B) 540 cal (C) 517.13 cal (D) 510 cal

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 Q.26 What can be concluded about the values of H and S from this graph?

(A) H > 0, S > 0 (B) H > 0, S < 0

(C) H < 0, S > 0 (D) H < 0, S < 0

Q.27 If Hvaporisation of substance X (l) (molar mass : 30 g/mol) is 300 J/g at it's boiling point 300 K, then
molar entropy change for reversible condensation process is
(A) 30 J/mol.K (B) – 300 J/mol.K (C) –30 J/mol.K (D) None of these

Q.28 Pressure of 10 moles of an ideal gas is changed from 2 atm to 1 atm against constant external pressure
without change in temperature. If surrounding temperature (300 K) and pressure (1 atm) always
remains constant then calculate total entropy change (Ssystem + Ssurrounding) for given process.
[Given : n2 = 0.70 and R = 8.0 J/mol/K]
(A) 56 J/K (B) 14 J/K (C) 16 J/K (D) None of these

Q.29 The enthalpy of tetramerization of X in gas phase (4X(g)  X4(g)) is – 100 kJ/mol at 300 K.
The enthalpy of vaporisation for liquid X and X4 are respectively 30 kJ/mol and 72 kJ/mol respectively.
S for tetramerization of X in liquid phase is – 125 J / K mol at 300 K.
What is the G at 300 K for tetramerization of X in liquid phase ?
(A) –52 kJ/mol (B) –89.5 kJ/mol (C) –14.5 kJ/mol (D) None of these

Q.30 The change in entropy of 2 moles of an ideal gas upon isothermal expansion at 243.6 K from 20 litre
until the pressure becomes 1 atm, is :
(A) 1.385 cal / K (B) –1.2 cal / K (C) 1.2 cal / K (D) 2.77 cal / K

Q.31 Standard entropy of X2, Y2 and XY3 are 60, 40 and 50 JK–1mol–1, respectively. For the reaction,
1 3
X 2  Y2  XY3 , H  30kJ to be at equilibrium, the temperature will be
2 2
(A) 1250 K (B) 500 K (C) 750 K (D) 1000 K

Q.32 When two equal sized pieces of the same metal at different temperatures Th (hot piece) and Tc(cold
piece) are brought into contact into thermal contact and isolated from it's surrounding. The total change
in entropy of system is given by
Tc  Th T2 (Tc  Th ) 2 (Tc  Th ) 2
(A) C ln (B) C ln (C) C ln (D) C ln
2Tc T1 2Th .Tc 4Th .Tc

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 SUBJECTIVE

3 5
Q.1 0.5 mole each of two ideal gases A (Cv = R) and B (Cv = R) are taken in a container and
2 2
expanded reversibly and adiabatically from V = 1 L to V = 4 L starting from initial temperature T = 300
K .
Find H for the process in (cal/mol).

Q.2 Pressure over 1000 ml of a liquid is gradually increases from 1 bar to 1001 bar under adiabatic
conditions. If the final volume of the liquid is 990 ml, calculate U and H of the process, assuming
linear variation of volume with pressure.

Q.3 One mole of a monoatomic gas behaving ideally is used as

working substance in an engine working in the cycle as shown
in the figure. The process AB, BC, CD and DA are respectively
reversible isobaric, adiabatic, isochoric and isothermal. The
ratio of maximum to minimum volume and temperature during
the cycle is 8 2 and 4 respectively. If the maximum T is 800
K
and  = 5/3. Calculate E ( in kJ) for the process BC.
Given R = 8.3 J/K-mol.

Q.4 One mole of an ideal gas at 300 K is heated at constant volume (V1) until it's temperature is doubled,
then it is expanded reversibly isothermally till it reaches the original pressure. Finally the gas is cooled
at constant pressure till system reached to the half of original volume (V1/2).
Determine total work done ( |w| ) in cal.
[Use : ln2 = 0.70 ; R = 2 Cal/ K. mol.]

Q.5 At 298 K, H°combustion (sucrose) = –5737 KJ/mol & G°combustion (sucrose) = –6333 KJ/mol.
Estimate additional non-PV work that is obtained by raising temperature to 310 K.
Assume rCP = 0 for this temperature change

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 ANSWER KEY
OBJECTIVE

Q.1 C Q.2 D Q.3 D Q.4 B Q.5 C Q.6 B Q.7 C

Q.8 A Q.9 B Q.10 C Q.11 D Q.12 C Q.13 A Q.14 C

Q.15 C Q.16 D Q.17 C Q.18 A Q.19 A Q.20 B Q.21 C

Q.22 A Q.23 C Q.24 D Q.25 C Q.26 A Q.27 C Q.28 C

Q.29 C Q.30 D Q.31 C Q.32 D

SUBJECTIVE
Q.1 – 900 calories

Q.2 U = 501 J ; H = 99.5 kJ

Q.3 E = 2.49 kJ

Q.4 60 cal

Q.5 24 kJ/mol

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