Physical Chemistry II

(CHE21M5)

Lecture #4:
2nd Law of Thermodynamics
“Entropy”
Elements Of Physical Chemistry, Peter Atkins & Julio de Paula, 5th
Ed, Pages 83-95
The 2nd Law: Entropy (S)
• Entropy is the measure of disorder in a thermodynamic system.
The more disorder, the higher the entropy. Energy is needed to
reverse a non-spontaneous process(S.I. Unit: J/K or J.K-1)
• It provides a measure of probability, spontaneous process has
This change is
higher probability. To determine if a process is spontaneous or
non spontaneous not. Will it happen by itself or does it need a boost?
Requires energy
• Solid atoms more organised (low entropy), gas molecules have
high entropy
High Entropy
Low Entropy

• 2nd law: 2nd Law of Thermodynamics states that if process A B

is spontaneous in an isolated system, the entropy of a
spontaneous system and its surrounding will never decrease
-Q
• Spontaneous: A process that does not need an outside of energy
to proceed
• The reverse is spontaneously impossible. But possible with an
external force/work
Mathematical Equations for 2nd Law:
• Total entropy of the overall isolated system: ∆Suniv = ∆Ssystem + ∆Ssurrounding ≥ 0
Is the reaction spontaneous?
ΔSsystem = n S (products) - n 𝑺 (reactants) 10 J heat absorbed 10 J heat released
By the hot tea By the hot tea
• Definition of a change in entropy for a system maintained at constant temperature
Tea at
and pressure going from state 1 to state 2: 45 ºC
𝟐 𝒒rev ∆𝑯
𝟏
dS = S2 – S1 = ∆Srev = 𝑻 =𝑻 (reversible system, equilibrium, q = ∆H) Surrounding
𝑺𝒚𝒔𝒕𝒆𝒎 𝑺𝒚𝒔𝒕𝒆𝒎
at 25 ºC
• That is, the change in entropy of a substance is equal to the energy transferred as heat
to it reversibly divided by the temperature at which the transfer takes place #Case 1: If Q = 10 J (system gains q)
∆Suniv = ∆Ssystem + ∆Ssurr

+ 10 𝐽 − 10 𝐽
∆Suniv = ∆Ssystem + ∆Ssurrounding + = -0,0021 J/K
45+273 25+273
• For a reversible process :∆Suniv = 0, therefore ∆Ssystem = -∆Ssurrounding (-ve ∆S, not spontaneous)

#Case 2: If Q = -10 J (system looses q)

𝒒(surr) − 10 𝐽 + 10 𝐽
Surrounding: ∆Ssurr = 𝑻𝑺𝒖𝒓𝒓
(heat supplied to the surrounding, +ve) + = 0,0021 J/K
45+273 25+273
−𝒒(sys) −∆𝑯 (+ve ∆S, spontaneous)
∆Ssurr = (-ve according to the system, at constant pressure)
𝑻𝑺𝒖𝒓𝒓 = 𝑻𝑺𝒖𝒓𝒓
Entropy of transition

The entropy of any transition is related to its enthalpy at that transition

and temperature
∆Hf
Entropy of formation: ∆Sf =
𝑻f
∆Hm
Entropy of melting: ∆Sm =
𝑻m
∆Hvap
Entropy of vaporization: ∆Svap=
𝑻𝒃
∆Hc
Entropy of combustion: ∆Sc=
𝑻
Full Table available at the back of the textbook. Remember that the
values will always be provided in a test
Reaction Standard Entropy Calculation
• Calculate the standard entropies for the following reactions at 25 °C.
See Table at the back of textbook for standard entropy values.

ΔSo = nΔSo (products) - nΔSo (reactants)

N2(g) + 3H2(g) → 2NH3(g)

∆S for Isothermal expansion

𝒒rev nRT ln(Vf/Vi)

 ∆S = =
𝑻 𝑻

∆U = q + w (∆U = 0 for Isothermal)

Therefore q = -w
W = -nRT ln(Vf/Vi) and q = nRT ln(Vf/Vi)
• T changes, P constant:
𝒅𝒒rev 𝒅𝒒rev 𝒑 𝒅𝑯 𝑇2 𝑪𝒑𝒅𝑻
∆S = dS = 𝑻𝑺𝒚𝒔𝒕𝒆𝒎
= 𝑻𝑺𝒚𝒔𝒕𝒆𝒎
= 𝑻𝑺𝒚𝒔𝒕𝒆𝒎
= 𝑇1 𝑻𝑺𝒚𝒔𝒕𝒆𝒎

𝑻𝟐
∆S = S(Tf) – S(Ti) = Cp ln
𝑻𝟏

• T changes, V constant:
𝒅𝒒rev 𝒅𝒒rev 𝒗 𝒅𝑼 𝑇2 𝑪𝒗𝒅𝑻
∆S = dS = = = = 𝑇1 𝑻𝑺𝒚𝒔𝒕𝒆𝒎
𝑻𝑺𝒚𝒔𝒕𝒆𝒎 𝑻𝑺𝒚𝒔𝒕𝒆𝒎 𝑻𝑺𝒚𝒔𝒕𝒆𝒎

𝑻𝟐
∆S = S(Tf) – S(Ti) = Cv ln 𝑻𝟏

ΔCp(reaction) = n Cp (products) - n Cp(reactants)

(Cp can be replaced with Cv)
 𝑻𝟐
Example 1 ∆S = S(Tf) – S(Ti) = Cv ln 𝑻𝟏

ΔCp(reaction) = n Cp (products) - n Cp(reactants)

Example 3
Entropy Changes of the Ideal Gas
𝒒
2nd Law of thermodynamics: S2 – S1 = ∆S =
𝒒 𝑻
2nd Law of thermodynamics: S2 – S1 = ∆S = Ideal Gases: PV = RT (per mole)
𝑻
Ideal Gases: PV = RT (per mole) dH = 𝑪𝒑𝒅𝑻
dU = 𝑪𝒗𝒅𝑻
1st Law of thermodynamics: dH = dq + PV
1st Law of thermodynamics: dU = dq + dw
Cv dT = dq – PdV Cp dT = dq + PV
dq = Cv dT + PdV dq = Cp dT - VdP
𝑹𝑻 𝑹𝑻
dq = Cv dT + dV dq = Cp dT - dP
𝑽 𝑷
𝒅𝒒 𝟏 𝟏 𝒅𝒒 𝟏 𝟏
(divide by T) : = Cv dT + R dV (divide by T) : = Cp dT - R dP
𝑻 𝑻 𝑽 𝑻 𝑻 𝑷
𝒅𝒒 𝒅𝑻 𝒅𝑽 𝒅𝒒 𝒅𝑻 𝒅𝑷
Intergrate: = Cv +𝑹 Intergrate: = Cp −𝑹
𝑻 𝑻 𝑽 𝑻 𝑻 𝑷

𝑻𝟐 𝑽𝟐 𝑻𝟐 𝑷𝟐
∆S = Cv ln + R ln ∆S = Cp ln - R ln
𝑻𝟏 𝑽𝟏 𝑻𝟏 𝑷𝟏

𝑽𝟐 𝑷𝟐
For Isothermal Expansion: S2 – S1 = ∆S = R ln For Isothermal Expansion: S2 – S1 = ∆S = - R ln
𝑽𝟏 𝑷𝟏
At constant volume, the second term is zero At constant pressure, the second term is zero
Entropy Calculations: Examples
Example 1: Calculate the entropies of vaporization in J K–1 mol–1 of the following substances, from their boiling points and
enthalpies of vaporization:
substance boiling point (K) Enthalpy Jmol-1 ∆Hvap 40,6
For H2O: ∆Svap= 𝑇 = 373 = 0,109 JK-1mol-1
∆H
∆S =
𝑻
H2O 373 40.6 ∆Hvap 29,4
For CHCl3: ∆Svap= = = 0,09 JK-1mol-1
𝑇 334
CHCl3 334 29.4
𝟓
Example 2: Calculate the entropy of 1 mole of hydrogen gas that is heated from 300 K to 1000 K with Cv = 𝟐R. The gas can
be treated as an ideal gas and at constant volume.
𝑻𝟐 𝑽𝟐
∆S = Cv ln
𝑇2
+ R ln
𝑉2
=
5
R ln
1000
+ 0 = 25 JK-1mol-1
∆S = Cv ln + R ln
𝑻𝟏 𝑽𝟏
𝑇1 𝑉1 2 300

Example 3

𝑻𝟐 𝑷𝟐
∆S = Cp ln - R ln
𝑻𝟏 𝑷𝟏
∆S during multiple phase transitions
The entropy of a system at a temperature T is related to its entropy at T = 0 K (-273 oC ) by
measuring its heat capacity Cp at different temperatures and evaluating the integral. The
entropy of transition for each phase transition that occurs between T = 0 K and the
temperature of interest must then be included in the overall sum.

Single step phase transitions at

constant temperature & pressure. The
entropy for a phase change is just the
heat (which is the reversible heat)
divided by the phase transition
temperature
∆Hm
Entropy of melting: ∆Sm = 𝑻
m
Entropy of vaporization: ∆Svap=
∆Hvap
𝑻𝒃

Transitioning from T1 (solid) to T2 (vapour)

∆S = heating ice + ice melting(water) + heating water + water evaporation + heating water
∆Ss (T1  Tm) + ∆Sm + ∆Sl (Tm  Tg) + ∆Svap + ∆Sg (Tg  T2)
∆S during phase transitions (ice  liquid  water vapour)

∆S = heating ice + melted ice + heating water + evaporation water + heating water
∆S = ∆Ss (T1  Tm) + ∆Sm + ∆Sl (Tm Tg) + ∆Svap + ∆Sg (Tg  T2)

∆H
∆S(at transition Temp.) = (melting at 0 oC, boiling at 100 oC)
𝑻
𝑻𝟐 𝑪𝒑 𝒅𝑻
∆S(heating) = 𝑻𝟏
(entropy change when the heat capacity varies with temperature)
𝑻

Entropy Change (ice vapour):

Zero (0) here

S2 – S1 = ∆S = refers to 0 K not
Celsius
Example 1

Notes:
- We begin at a solidliquid transition
temperature T1
- Temperature does not go above 100 oC ,
therefore liquidgas transition does not
take place

100 oC =

100 oC) =
Example 2

Calculate the change in entropy of the system when 15.0 g of ice at

−12.0 °C is converted to water vapour at 105.0 °C at a constant pressure
of 1 bar.

𝑻𝟐 𝟐𝟕𝟑
1. Ice melts: ∆S = Cp ln = 37,6 x ln 𝟐𝟔𝟏 = 𝟏, 𝟔𝟗 Notes:
𝑻𝟏
∆H 𝟔𝟎𝟏𝟎 - We start at a temperature below melting
2. Entropy of melting: ∆S = = = 22,01
𝑻 𝟐𝟕𝟑
𝟑𝟕𝟑 point, so the solid must first melt  liquid
3. Water boils: ∆S = 75,3x ln 𝟐𝟕𝟑 = 23,50 - We end with temperature above boiling
∆H 𝟒𝟎𝟕𝟎𝟎 point, therefore entropy of vaporization
4. Water evaporates: ∆S = 𝑻 = 𝟑𝟕𝟑 = 109,11
𝟑𝟕𝟖 must be included (liquidgas transition )
5. Water in vapour state: ∆S = 33,6x ln 𝟑𝟕𝟑 = 0,45
∆S = 1,69 + 22,01 + 23,50 + 109,11 + 0,45 = 156,7 J K−1 mol−1
For 15 g of ice: n = 15/18 = 0,83 mol
Therefore ∆S = 0,83 mol x 156,7 J K−1 mol−1 = 130,1 J/K
Mole Fraction Calculations
Mole fraction is a unit of concentration, defined to be equal to the number of moles of a
component divided by the total number of moles of a solution. Because it is a ratio, mole
fraction is a unitless expression. The mole fraction of all components of a solution, when added
together, will equal 1
n n
For a container with 2 components: X1= 1 X2 = 2 and nT = n1 + n2 + …
n1+n2 n1+n2

X is a “fraction 𝑜𝑓" and cannot be more than 1: 𝑋𝑇 = 𝑋1+ 𝑋2 + …= 1

Example: If a mixture of gases contains 7,5 g H2, 3,25 g O2 and 5,55 g N2, What is the mole
fraction of each gas?
𝑚
1. Determine number of moles: n = Take note if moles
𝑀
7,5 𝑔 3,25 5,55 or mass is given
2. n(H2) = = 3,75 n(O2) = = 0,10 n(N2) = = 0,40
2𝑔/𝑚𝑜𝑙 32𝑔/𝑚𝑜𝑙 14𝑔/𝑚𝑜𝑙
n(gas) n(gas) n(gas)
3. X(gas) = = =
n(H2)+n(O2)+n(N2) 3,75+0,1+0,4 4,25
3,75 0,1 0,4
4. Mole Fractions: X(H2) = = 0,882 X(O2) = = 0,024 X(N2) = = 0,094
4,25 4,25 4,25
5. 𝑋𝑇 =0,882 + 0,024 + 0,094 ≈1
∆S of ideal gas mixing ∆S = Cv ln
𝑻𝟐
𝑻𝟏
+ nR ln
𝑽𝟐
𝑽𝟏

• Consider two gases A and B mixing together, ∆S increases when two ideal
gases mix in an isolated system Assume T and P of gas A & B are the same
No transfer of heat
• 𝑋𝑇 = 𝑋𝐴+ 𝑋𝐵 + …= 1 and nT = nA + nB + … Volume changes but no work is done
Entropy increases
𝑃𝑉𝑖
• ni = (PV = nRT)
𝑅𝑇
𝑃𝑉𝐴
𝑛𝐴 𝒏𝑨 𝑽𝑨
• Mole fraction of A: 𝑿𝑨 = = = 𝑅𝑇
𝑃𝑉𝑇 =
𝑛𝐴+ 𝑛𝐵 𝒏𝑻 𝑽𝑻
𝑅𝑇
𝑃𝑉𝐵
𝑛𝐵 𝒏𝑩 𝑽𝑩 Gas A Gas B
• Mole fraction of B: 𝑿𝑩 = = = 𝑅𝑇
𝑃𝑉𝑇 = nA ,VA , P, T nB ,VB , P, T
𝑛𝐴 + 𝑛𝐵 𝒏𝑻 𝑽𝑻
𝑅𝑇
𝑽𝑻 𝒏𝑻
Entropy change: ∆Si = niRln = niRln
𝑽𝒊 𝒏𝒊
𝑛
For two gases: ∆ST = 𝑖=1 ∆S = ∆SA + ∆SB
VT = VA + VB
𝑉 𝑉𝑇
Therefore: ∆ST = n𝐴Rln 𝑇 + n𝐵Rln nT = nA + nB
P, T
𝑉𝐴 𝑉𝐵
𝑽 𝟏 𝑽𝑻 𝑉𝑇 1
𝑿 = 𝒊
OR = 𝑛 𝑛 𝒏
 𝒊 𝑽𝑻 𝑿𝒊 𝑽𝒊 𝑖=1 ni R ln 𝑉 = 𝑖=1 ni R ln = -R 𝒊=𝟏 ni ln 𝑿𝒊
𝑖
𝑋𝑖
Examples: ∆S of ideal gas mixing
Example 1: Calculate the entropy of mixing per mole of air,
taking the composition by volume to be 79% N2, 20% O2,
and 1% Ar.
Example 2: One mole of each gas of H2 , O2 and N2, at
25 °C and 1 atm pressure, are mixed isothermally;
the final total pressure is 1 atm. Calculate ΔS, on the
assumption of ideal behavior.

Each gas has 1 mole and therefore all have same

mole fraction
X(gas) = 1mole/3mole = 0.333
N(total) = 3 moles

𝟏
𝒏
𝒊=𝟏 ni R ln
𝟏 Method 1: ΔS = 𝒏𝒊=𝟏 ni R ln
𝑿𝒊 𝑿𝒊
= [1 x 8.314 x ln(1/0.333)] x 3 = 27,43 J K−1 mol−1
𝑽𝑻
∆Si = niRln 𝑽𝒊 𝐧
M𝐞𝐭𝐡𝐨𝐝 𝟐: ∆Si = niRln 𝐧𝐓
𝐢
ΔS (hydrogen) = 1x8,314xln(3/1) x 3 = 27,40 J K−1 mol−1