Chemistry CY1001

K. Mangala Sunder*
Professor, Department of Chemistry
Indian Institute of Technology Madras
Chennai, India

*mangal@iitm.ac.in; mangalasunderk@gmail.com
A “ Thermodynamic “ acknowledgment found in a text book.
Chemistry, Principles and Reactions by
William L. Masterton and Cecile N.Hurley. Saunders,1989.
To Loris and Jim: (Children of the Author, perhaps??)
For their understanding when entropy was high;
And their encouragement when energy was low.
 Lecture 3

First law - introduces the concept of internal energy.

Second law - introduces the concept of entropy – identifies
spontaneous changes among permissible changes.
1. The energy of the universe is constant; the entropy tends to a
maximum.
2. The entropy of an isolated system increases in the course of a
spontaneous change.

Clausius formulation of the second law:

It is impossible for an engine to perform work by cooling a portion of
matter to a temperature below that of the coldest part of the
surroundings.
 Rudolf Clausius (1822-1888) William Thomson (1824-1907)
- given later the title Lord Kelvin

Second law of thermodynamics –

Result of research on steam engines.

Worked on reversible steam engine –

and on the efficiency of conversion of
French Engineer heat into mechanical work.
Sadi Carnot
(1796-1832) His result: Every engine operates at an
efficiency lesser than or equal to that
of an idealized reversible engine.
 Carnot Cycle – q/T – T diagram.

Carnot Cycle – P –V diagram. (adiabat is steeper than isotherm)

Carnot Cycle – q / T – T diagram.
1. Isothermal expansion. P1V1T1 à P2V2T1

δq + δw = dU = 0
(No change in internal energy, because the process is at constant
temperature)

∴δq = + PdV
nRT
=+ dV
V
δq nR
=+ dV
T V
P2 V2
δq V2
∫
P1V1
T
= nR ln
V1
Positive quantity as V2 > V1.
Heat is absorbed at T1. (source temperature)
 Carnot Cycle – q / T – T diagram.
Step 2
Adiabatic: P2V2T1 ---> P3V3T2

dU = δq + δw = −PdV
δq = 0

Note that T is also changed.

dU = Cv dT Heat capacity at constant volume.

ΔU = Cv ( T2 − T1 )
Carnot Cycle – q / T – T diagram.
Step 3
Isothermal compression: P3V3T2 P4V4T2

δq + δw = dU = 0
nRT
δq = −δw = PdV = dV
V
T = T2
P4 V4
δq V4 Negative since heat is given out (V < V ).
∴ ∫ = nR ln = 4 3

P3 V3
T2 V3

Note: Heat is given out at T2 (sink temperature)

Carnot Cycle – q / T – T diagram.
Step 4
Adiabatic compression: P4V4T2 P1V1T1

dU = δw + δq
δq = 0
⇒ ΔU = CV ( T1 − T2 )
Things to remember
Internal energy is a function of temperature.

∴ ( ΔU ) + ( ΔU ) = 0
step II step IV
U

Since T1 > T2 Δ U is zero for isothermal processes, step I and III

.
 (ΔU)overall = 0 = ( Δw + Δq )overall
δq δq q1 q 2
Δw = −Δq ⇒ +∫ +∫ = +
T1 T2 T1 T2
V2 V V V
Δw = nRT1 ln + nRT2 ln 4 = nRT1 ln 2 − nRT2 ln 2
V1 V3 V1 V1
V2
= nR ( T1 − T2 ) ln
V1
Heat absorbed = q1 at T1
Heat discarded = q 2 at T2

Efficiency of engine
V2
nR ( T1 − T2 ) ln
Heat converted to work q1 − q 2 V1 T1 − T2
= = = =
Total Heat absorbed q1 V2 T1
nRT1 ln
V1

Never one, except when T2 = 0.

 From the q/T – T diagram of Carnot cycle, note:

q1 − q2 T1 − T2 q T
= ⇒ 1− 2 = 1− 2
q1 T1 q1 T1
q2 q1
=
T2 T1

q1 is the heat absorbed by the system; it is positive.

q2 is the heat given out by the system; it is negative.

q2 q1 q1 q2
∴ = ; or, − = 0; for a reversible process,
T2 T1 T1 T2
q
is a state function!! It is associated with ENTROPY.
T
 The Second Law of thermodynamics:

• The entropy of an isolated system increases as a

result of spontaneous process. In a reversible cyclic
process, the entropy of an isolated system does not
change.

• An equivalent statement: The entropy of the

Universe is never decreasing.

• Clausius Statement: It is impossible for a system to

undergo a cyclic process with the only changes
being that heat flows into the system from a cold
reservoir and an equivalent amount of heat goes
from the system to the hot reservoir.
Entropy: Useful Relations

Definition of Entropy change: Clausius inequality

S is a state function – independent of path from state A --> B

(reversible or NOT)
For a reversible process:

dq rev
ΔS = ∫
A→B
T
For an irreversible process:

dqirrev
∫
A →B
T
< ΔS
In words: The integral

B
dq
∫A T
Is equal to the entropy change if the process is reversible and is less than
the entropy change if the process irreversible.
 Entropy Change:
Change of phases (change of state of aggregation)

solid ⎯⎯⎯⎯
latent heat
of fusion
→ liquid ⎯⎯⎯⎯⎯
latent heat
of vaporisation
→ gas(vapour)
( melting or evaporation at a fixed temperature)
- the two phases in equilibrium during the process:

Temperature is constant:

B B Δ fus H
dq rev 1 Δ fusS =
∫A T = T A∫ dq rev Tfus
Δ vap H
ΔH Δ vapS =
= Tvap
T
Ideal Gases:
Expansion of an ideal gas isothermally.
First law:
V2
q rev = nRT ln
V1
dq rev 1
∴ΔS = ∫ = q rev
T T
V2
= nR ln
V1
V2
ΔS = nR ln
V1
Positive for expansion, negative for compression.
Expansion of an ideal gas -
From (P1 , V1 , T1) to (P2 , V2 , T2)

x
(P1, V1, T1)

x
(P2, V2, T2)

Design this as a sum of two processes.

1. Isothermal expansion from P1 , V1 to P2’ , V2 at constant temperature T1
2. Change of temperature at V2 from P2’ , V2 , T1 to P2 , V2 , T2
 V2
1. ΔSI = nR ln
V1
T2 T2
dq rev dT
2. ΔSII = ∫ = nCV,m ∫
T1
T T1
T
T2
= nC V,m ln
T1
ΔSoverall = ΔSI + ΔSII
T2 V2
= nC V,m ln + nR ln
T1 V1
(Ideal gas, assumed heat capacity as independent of temperature)
Entropy change during free expansion:

V1 ,P1 ,T1 V2 , vacuum

V1 → ( V1 + V2 ) Expansion against zero pressure.

No heat change. No internal energy change.

ΔU = 0!
Δw = 0!
Δq = 0!
V1 + V2
However ΔSsystem = nR ln
V1

Process is irreversible. See clearly how Δq does NOT give

entropy change for the system.
Entropy of mixing of ideal gases:

n1 ,V1 ,T n 2 ,V2 ,T Before mixing

gas PI gas PII

n1 ,n 2 After mixing

P
V1 + V2
ΔS1 = n1R ln
V1
V1 + V2
ΔS2 = n 2 R ln
V2
Two ideal gases at the same temperature and pressure:
PV1 = n1RT
PV2 = n 2 RT
n1 n 2 V1
⇒ = or = x1
V1 V2 V1 + V2
n1
=
n1 + n 2
x1 − mole fraction of gas 1
V2 n2
likewise = x2 =
V1 + V2 n1 + n 2
x 2 − mole fraction of gas 2
ΔS = ΔS1 + ΔS2
1 1
= + n1R ln + n 2R ln
x1 x2
= − [ x1R ln x1 + x 2 R ln x 2 ]( n1 + n 2 )

Question for you ?

a) How would you generalize this to several gases [ n1 at v1, n2 at v2, n3 at v3

etc… mixing to a final volume v = v1 + v2 + v3 +…. ]?
b) What is the entropy of mixing of two gases n1 at V and n2 at V, mixing and
remaining in the same volume V ?
Q3 What is the entropy change when an ideal gas at volume V (n moles)
is mixed with the same gas ( again volume V1 n moles ) so that the final
volume is 2V ?

n moles n moles
V gas n1 V gas n1
mix

Think about the answer before blindly applying the formula.

Trouton’s rule

Empirical observation

Table 4.1 (Atkins) seventh edition.

Standard entropies of phase transitions ΔS

For a large number of liquids at their normal boiling point.

ΔS ~ 85 JK-1mol-1

Thus:

ΔH (approximate) for Br2, boiling point 59.2o.C

ΔH ~ DS X T(K) ~ 332.4K X 85 JK-1 mol-1

» 28 kJ mol-1

Experimental ~ 29.4 kJ mol-1

End of the Lecture. Thank You.