CHEMISTRY (CY11003)

Autumn 2020 -2021

LECTURE – 6
(14 th December)

Please do NOT CHAT Among Yourselves While

the Class is On. Department of Chemistry,
Indian Institute of Technology Kharagpur
Statistical Definition of Entropy: S = kB ln W

∆ S = nR ln(V2/V1)
The direction of spontaneous change is
from a situation in which the gas is in V1
to one in which it is in V2
That is, from a state with low probability of
occurring to one of a maximum probability.
When molecules are randomly and uniformly mixed
The direction of spontaneous change is from a less
probable state to a most probable state

Gas A Gas B

Ideal gas mixture ΔH = 0 Ideal solution

The Carnot Heat Engine: (contd)
For the Carnot cycle, ∆Ucy = 0

qH > 0, w < 0, qC < 0 TH > TC

wcy = – R(TH – TC) ln(V2/V1)

qH = RTH ln(V2/V1) ε = (TH – TC ) /TH = 1 – TC/TH

Thermodynamic efficiency (ε) can never be equal to 1 (or 100%)

because TC cannot be zero and TH cannot be infinite
Refrigeration: •Heat flows from a hot body to a cold body

• But if work is applied, heat can be made to

flow from a cold body to a hot body

−qH = qC + w COP = Coefficient of performance

qH is negative COP = qC /w

ε = w/|qH| = 1 – TC/TH => TC/TH = 1 − w/|qH|

TC/TH = (|qH| − w)/|qH| TC/TH = |qC|/|qH| TH/TC = |qH|/|qC|

(|qH| − |qC|)/|qC| = w/|qC| = (TH − TC)/TC

COP = |qC| /w = TC/(TH − TC)

When TC = 273 K and room temp. (TH) = 293 K , COP ≈ 14

Air Conditioners: COP = |qC| /w = TC/ (TH − TC)

Heat Pumps: COP = |qH| /w = TH/ (TH − TC)

Carnot Cycle:

For the reversible cyclic processes, ∆U = 0 , q ≠ 0, w ≠ 0 qrev/T = ?

qH/TH = n RTH ln(V2/V1) /TH = n R ln(V2/V1)

qC/TC = ‒ n RTC ln(V2/V1) /TC = ‒ n R ln(V2/V1) qH/TH + qc/TH = 0

∑qi/Ti = 0 qi /Ti ≡ ∆Si ∑∆Si = 0 => ∆Scy = 0

=> S is a state function
Entropy Function:
Entropy Change in the Surroundings:
∆ S = qrev/T or dS = dqrev/T (dqsurr )rev = (dqsurr )irrv = dqsurr

For irreversible expansion, qirrv < qrev Surrounding is very large compared
to system
∆ S = qrev/T > qirv/T
dSsurr = dqsurr / Tsurr
But ∆Srev = ∆Sirrv = ∆S => ∆S > qirrv/T ∆ Ssurr = qsurr / Tsurr
Entropy Change of the Universe:

∆Suniv = ∆Ssys + ∆Ssurr or ∆Suniv = qsys / T + qsurr / T

∆Suniv = nR T ln(V2/V1)/T + [‒ nR T ln(V2/V1)]/T = 0

If the expansion was irreversible, ∆Ssys = nR ln(V2/V1)

But no work is done in this process, w = 0

So no heat is exchanged between system and surroundings, q = 0
=> ∆Ssurr = qsurr /T = 0

∆Suniv = ∆Ssys + ∆Ssurr ≥ 0

∆Suniv = ∆Ssys > 0 => ∆Suniv ≥ 0, Clausius inequality

This is true for any isolated system; => The Second Law of Thermodynamics
Entropy Change Due to Phase Transitions:

* Phase changes occur at a constant pressure (P) and

temperature (T);
* During phase change at constant P and T, heat (qp) is
absorbed/expelled by the system reversibly: qrev = ∆H

Entropy of fusion, ∆fusS = ∆fusH/Tf

Entropy of vaporization , ∆vapS = ∆vapH/Tb ∆vapS > > ∆fusS

Different liquids have same molar entropy of vaporization (~ 88 J K−1 mol−1);

=> Trouton’s Rule
Entropy Change Due to Mixing of ideal Gases:

For Gas A:
∆ SA = nA R ln(VA+VB)/VA

For Gas B:
∆ SB = nB R ln(VA+VB)/VB

V = VA+VB; n = nA+ nB; => xA = nA/(nA+ nB ); xB = nB/(nA+ nB)

∆ Smix= ∆SA + ∆SB = nARln(VA+VB)/VA + nBRln(VA+VB)/VB

∆ Smix= nAR ln(nA + nB)/nA + nBR ln(nA + nB)/nB

∆ Smix= − nARln xA − nBRln xB ∆ Smix = − R (nAln xA + nBln xB)

∆ Smix= −R ∑ni ln xi ∆ Smix= −nR ∑xi ln xi => ∆ Smix > 0
The Second Law of Thermodynamics:
∆ Suniv = ∆Ssys + ∆Ssurr ≥ 0
“The energy of the universe is constant, but the
entropy increases toward a maximum.” (Clausius)

“The entropy of an isolated system increases in an

irreversible process and remains unchanged in a
reversible process”

“It is impossible in any way to diminish the entropy

of a system of bodies without thereby leaving behind
changes in other bodies.” (Max Plank)
Entropy Change Due to Heating:
If the temperature of a system is raised from T1 to T2 at
constant pressure without any phase change

dS = dqrev/T ∆ S = ∫qrev/T ∆ S = ∫dH/T ∆ S = ∫CP dT/T

∆ S = ∫CP dln T ∆ S = CP ln (T2 / T1) ∆ S = n CP,m ln (T2 / T1)

For a perfect solid, Lim S = 0 <= Third-law or absolute entropies

T→ 0 K

SO = kB ln W = kB ln 1 = 0 => ∆ S = ST − SO = ∫CP dln T

ST = ∫CP dln T
Entropy as a Function of Temperature and Volume:
S = S(T, V) U = U(T, V)
dS = (∂S/∂T)V dT + (∂S/∂V)T dV dU = (∂U/∂T)V dT + (∂U/∂V)T dV

dqrev = dU + PdV or, TdS = dU + PdV dU = CV dT + (∂U/∂V)T dV

dS = (1/T) dU + (P/T)dV => dS = (CV /T) dT + (1/T)[P + (∂U/∂V)T ]dV

(∂S/∂V)T = (1/T)[P + (∂U/∂V)T ] (∂S/∂T)V = CV /T CV /T is always positive

(∂2S/∂V∂T) = 1/T (∂CV /∂V) = 1/T (∂2U/∂V∂T) ∆ S = ∫CV dT/T

(∂2S/∂T∂V) = 1/T [(∂P/∂T)V + (∂2U/∂T∂V) − 1/T2 [P + (∂U/∂V)T]

(∂2S/∂V∂T) = (∂2S/∂T∂V) (∂2U/∂V∂T) = (∂2U/∂T∂V) ∆ S = ∫CV dln T

P + (∂U/∂V)T = T (∂P/∂T)V (∂U/∂V)T = T(∂P/∂T)V ‒ P ∆ S = CV ln (T2 / T1)

=> (∂S/∂V)T = (∂P/∂T)V = α/κ (∂S/∂V)T = (∂ P/∂T)V

κ is always positive; also α is positive for majority of substances,
dS = (CV /T) dT + α/κ dV except for water between 0 and 4 oC;
Entropy as a Function of Temperature and Pressure:
Entropy as a Function of Temperature and Pressure:

H = H(T, P) S = S(T, P)

dH = (∂H/∂T)P dT + (∂H/∂P)T dP dS = (∂S/∂T)P dT + (∂S/∂P)T dP

CP /T is always
dH = CP dT + (∂H/∂P)T dP (∂S/∂T)P = CP /T positive

dU = dH − PdV − VdP ∆ S = ∫CP dT/T ∆ S = CP ln (T2 / T1)

TdS − PdV = dH − PdV − VdP (∂2S/∂P∂T) = 1/T (∂ CP /∂P)T = 1/T (∂2H/∂P∂T)

dS = (1/T) dH − (V/T)dP => dS = (CP /T) dT + (1/T)[(∂H/∂P)T − V]dP

(∂S/∂P)T = (1/T )[(∂H/∂P)T − V] (∂2S/∂P∂T) = (∂2S/∂T∂P)

(∂2H/∂P∂T) = (∂2H/∂T∂P)
(∂2S/∂T∂P) = 1/T [(∂2H/∂T∂P) − (∂ V/∂T)P] − (1/T )[(∂H/∂P)T − V]

(∂H/∂P)T − V = − T (∂ V/∂T)P (∂H/∂P)T = V − T (∂ V/∂T)P (∂V/∂T)P = α V

dS = (CP /T) dT − α V dP => (∂S/∂P)T = − α V (∂S/∂P)T = − (∂ V/∂T)P

∆ S = − ∫ α V dP Or, ∆ S = − α V (P2 − P1) For solid and liquid (∂S/∂V)T = (∂ P/∂T)V

Thank you