Physical chemistry

Nghiem Thi Thuong

School of Chemical Engineering, HUST
Main content of the course

Chapter 1. Aspect of Thermodynamics

Chapter 2. Properties of mixtures
Chapter 3. Surface phenomena
Chapter 4. Adsorption
Chapter 5. Polymer
Chapter 6. Dispersions
Asssessment and exams

Mid-term grade

- Attendance: maximum 1 point/5 lectures

- Discussion/Exercise: maximum 1 point
- Mid-term test: paper test (multi-choice questions, problems)

Final grade

- Final test: paper test (multi-choice questions, problems)

Overall grade = 30% mid-term grade+ 70% final test

Some guidances to perform the couse succesfully

- Reading text book before class

- Follow the lectures carefully
- Do exercise and review lectures

Text books
- Elements of Physical Chemsitry (6th edition), P.Atkins and J.de
Paula, OUP Oxford, (2013)
Chapter 1. Aspects of Thermodynamics

First law of thermodynamics

Chapter 1. Thermodynamics

What is work?

Compression
Pexternal

Pressure-volume or mechanical work (W)

For a expansion $"

Expansion
W!"# = − $ P"%& . dV
$!

W'!!" = − P"%& . ∆V Ideal gas

V1 is volume of initial state; V2 is volume of final state

Sign of work
* If V2> V1: expansion occurs, work of expansion
is negative (work done by the system)
* If V2< V1: compression occurs, work of
compression is positive (work done on the system)

Unit of work: 1 J = 107 erg; 1 calorie = 4.184 J

V1 is volume of initial state; V2 is volume of final state

Chapter 1. Aspects of Thermodynamics

What is work?

For reversible process For irreversible process

P P

(2) (1)
P1 P1 W'!!" = −P"%& . ∆V

PV=const

P2 P2

V1 V2 V V1 V2 V

$"
𝑉( 𝑃)
W!"# = − $ P"%& . dV = −nRTln = −nRTln
$! 𝑉) 𝑃(

https://www.youtube.com/watch?v=sYe0ulf428w
Chapter 1. Thermodynamics

What is heat?
Heat is one form of energy changes between
the system and the surroundings which results
from the difference in the temperature of the
system and the surroundings

Chaotic
motion

Sign of heat
Q (+) positive: heat absorbed by the system
Q (-) negative: heat evolved/produced by the system

Unit of heat: 1 calorie = 4.184 J = 4.184.107 erg

Chapter 1. Thermodynamics

First law of thermodynamics

"The change in internal energy (U) of a system is equal to the heat added to the
system (Q) plus the work done on the system (W)"

Work done on the system

∆U = Q + W
Heat absorbed
Internal energy change in the system

or ∆U = Q - Pex∆V

For a small change (infinitesimal) 𝑑U = dQ − ' PdV

Chapter 1. Thermodynamics

Enthalpy of a system
Enthalpy of a system is a state function which is defined as: H = U + PV
work
At constant pressure
∆H = H2-H1 = ∆U + P∆V
increase in internal energy

change in enthalpy
Sign of enthalpy changes of a process
∆H > 0: heat absorbed by the system Endothermic process
∆H < 0: heat evolved from by the system Exothermic process

For expansion of ideal gas at constant pressure ∆H = H2-H1 = ∆U + nR∆T

For a reaction at constant temperature ∆H = H2-H1 = ∆U + ∆nRT
Chapter 1. Thermodynamics

Enthalpy of a system
"Enthalpy a change accompanied by a certain process is called the enthalpy of that
process. Thus enthalpy of evaporation (∆H"#./- ) means the change in the enthalpy
involved when one mole of the substance gets converted from the liquid state into the
vapor state. The enthalpies of fusion and sublimation have similar meanings" (Ref)
-
Enthalpy of formation (∆H*,, ) of a substance is the enthalpy of the reaction to from 1
mole of the substance from its most thermodynamically stable elements
-
Enthalpy of formation (∆H*,, ) of CO2
C(gr) + O2 (g) = CO2 (g)

-
Enthalpy of combustion (∆H0,, ) of a substance is the enthalpy change which occurs
when 1 mole of the substance burns completely in oxygen
-
Enthalpy of combustion (∆H*,1(34) ) of C (graphite)
C(gr) + O2 (g) = CO2 (g)
Chapter 1. Thermodynamics

Second law of thermodynamics

Chapter 1. Thermodynamics

Spontaneous processes

All spontaneous processes are irreversible processes

Chapter 1. Thermodynamics

Reversible and irreversible processes

Very slow
All states the system passed through are equilibrium states

initial state final state

Chapter 1. Thermodynamics

Entropy state function

Entropy is a state function which measures the randomness and the amount
of disorder of a system

Entropy is a function of W (number of microstates of a gas in a macrostate):

S = k.lnW (Boltzmann equation)
Entropy has characteristic of an extensive property, thus:
Stotal = S1+ S2 + ...+Si (Si: entropy of component i)
Unit of entropy: cal/K.mol or J/K.mol or J/K.g or cal/K.g
Chapter 1. Thermodynamics

Entropy change of a system

For reversible process

Entropy change of a system is defined as equal to the heat absorbed reversibly by the
system divided by the temperature at which the heat is being absorbed
𝑄467 𝑑𝑄467
∆𝑆 = 𝑆( − 𝑆) = 𝑜𝑟 𝑑𝑆 =
𝑇 𝑇
For irreversible process
𝑄,4467 𝑑𝑄,4467
∆𝑆 > 𝑜𝑟 𝑑𝑆 >
𝑇 𝑇

Mathematical expression of second law

𝑄 𝑑𝑄
∆𝑆 ≥ 𝑜𝑟 𝑑𝑆 ≥
𝑇 𝑇
Chapter 1. Thermodynamics

Entropy change of the universe

the universe = system + surroundings

∆𝑆89,764:6 = ∆𝑆:;:<6= + ∆𝑆:844-89>,93:

For reversible processes: entropy change of the universe is zero

For irreversible processes: entropy change of the universe is positive
Chapter 1. Thermodynamics

Entropy change of the universe

the universe = system + surroundings

∆𝑆89,764:6 = ∆𝑆:;:<6= + ∆𝑆:844-89>,93:

For reversible processes: entropy change of the universe is zero

For irreversible processes: entropy change of the universe is positive

Entropy as Criterion of spontaneity

∆𝑆89,764:6 = ∆𝑆:;:<6= + ∆𝑆:844-89>,93: = 0 for a reversible process
∆𝑆89,764:6 = ∆𝑆:;:<6= + ∆𝑆:844-89>,93: > 0 for an irreversible process

If the system is considered as isolated with the surroundings, ∆𝑆!"!#$%

could be used as criterion of spontaneity
∆𝑆:;:<6= = 0 for a reversible process
∆𝑆:;:<6= > 0 for an irreversible process
Chapter 1. Thermodynamics

Entropy change of some reversible processes

+ For a reversible phase transition at standard phase transition temperature

𝑄!"#
∆𝑆 =
𝑇

(for examples: fusion, vaporization, sublimation, crystalline transition)

+ For reversible processes at constant pressure and constant volume (without phase
transition)
T2 T2
δQ Cp
ΔS = ∫ = ∫ dT
T
T T1
T
1

T2
Cv
ΔS = ∫ dT
T
T
1
Chapter 1. Thermodynamics

Entropy change of some reversible processes

For a reversible expansion of gas with a heat supplied

For an isothermal process

For a reversible process at constant

pressure (isobaric process)

For a reversible process at constant

volume (isochoric process)
Chapter 1. Thermodynamics

Entropy change of irreversible processes

ΔSirrev
1 2

ΔS1,rev ΔS2,rev ΔS3,rev

ΔS = ΔS1 + ΔS2 + ΔS3

Example: Calculate entropy changes of a system and surroundings when 1

mol of water condensed at -10oC at a constant pressure of 1 atm.
- Surrounding temperature is kept constantly at -10oC
- Heat of fusion of ice water is 6024 J/mol at -10oC
- Heat capacity of liquid and ice water
Cop(H2O,liquid) = 76.1 J/K.mol, Cop (H2O,solid) = 37.1 J/K.mol
Chapter 1. Thermodynamics

Entropy change of irreversible processes

ΔSo (irrev)
H2O (liquid, -10oC) H2O (solid, -10oC)

ΔSo1(rev) ΔSo3 (rev)

H2O (liquid, 0oC) H2O (solid, 0oC)

ΔSo2 (rev)

273
Cp,l
ΔS1 = ∫
263
T
dT ΔSsystem = ΔS1 + ΔS2 + ΔS3 = -41,2 J.K-1

ΔHkt,273 −ΔHnc,273 ΔHmt ΔHnc,263

ΔS2 = = ΔSmt = = = 42,84J.K −1
273 273 263 263
263
Cp,r
ΔS3 = ∫
273
T
dT ΔSuniverse = ΔSsystem + ΔSsourroundings = 1,64 J.K-1
Chapter 1. Thermodynamics

The Helmholtz and Gibbs

energy
Chapter 1. Thermodynamics

∆𝑆89,764:6 = ∆𝑆:;:<6= + ∆𝑆:844-89>,93: = 0 for a reversible process

∆𝑆89,764:6 = ∆𝑆:;:<6= + ∆𝑆:844-89>,93: > 0 for an irreversible process

Focus on the system only

 Chapter 1. Thermodynamics

𝑑𝑄
From the second law: 𝑑𝑆 ≥
𝑇

dU
at a constant volume dS ≥ → TdS ≥ 𝑑𝑈 𝑑𝑈 − 𝑇dS ≤ 0
T
𝑑𝑈?,@ ≤ 0

"The internal energy must decrease when entropy and volume of the
system are constant"

dH
at a constant pressure dS ≥ → TdS ≥ 𝑑H 𝑑𝐻 − 𝑇dS ≤ 0
T
𝑑𝐻?,A ≤ 0
"The enthalpy must decrease when entropy and pressure of the
system are constant"

These are new criteria for spontaneity of process

Chapter 1. Thermodynamics

At constant volume 𝑑𝑈 − 𝑇dS ≤ 0

At constant pressure 𝑑𝐻 − 𝑇dS ≤ 0

If temperature (T) also remains constant

𝑑𝑈 − 𝑇dS = 𝑑 𝑈 − 𝑇𝑆 = 𝑑𝐹 New thermodynamics

quantities
𝑑𝐻 − 𝑇dS = 𝑑 𝐻 − 𝑇𝑆 = 𝑑𝐺

Gibbs energy G = H-TS

Helmholtz energy F = U-TS

Two more new criteria of spontaneous change 𝑑𝐹B,@ ≤ 0 𝑎𝑛𝑑 𝑑𝐺B,A ≤ 0

Chapter 1. Thermodynamics

Gibbs free energy (G) G

𝑑𝐺B,A ≤ 0

at constant T and P, chemical reaction

are spontaneous in the direction of
decreasing Gibbs energy Gmin
𝑑𝐺 = 𝑑𝐻 − 𝑇𝑑𝑆 Equilibrium state

G can be used to explain why some endorthermic reaction

could take place spntaneously

A spontaneous endothermic reaction dH >0, dG <0 then dS >0

Chapter 1. Thermodynamics

Helmholtz energy (F)

𝑑𝐹B,@ ≤ 0

at constant T and V, chemical reaction

are spontaneous in the direction of F
decreasing Helmholtz energy

𝑑𝐹 = 𝑑𝑈 − 𝑇𝑑𝑆

Fmin

Equilibrium state
Chapter 1. Thermodynamics

Maximum work done by system

𝑑𝑈 = 𝑑𝑄 − 𝑃𝑑𝑉 + 𝑑𝑊′

𝑑𝑄 ≤ 𝑇𝑑𝑆
Combine these two equations

𝑑𝑈 ≤ 𝑇𝑑𝑆 − 𝑃𝑑𝑉 + 𝑑𝑊 C 𝑜𝑟 −𝑑C 𝑊 ≤ −𝑑𝑈 + 𝑇𝑑𝑆 − 𝑃𝑑𝑉

−𝑑𝑊 ≤ −𝑑𝑈 + 𝑇𝑑𝑆 − 𝑃𝑑𝑉

Two normal conditions of change

+ T, V=const −𝑑𝑊=DE ≤ −𝑑𝑈 + 𝑇𝑑𝑆 = − 𝑑𝐹 → −𝑊=DE ≤ −∆𝐹

+ T, P=const −d𝑊=DE ≤ −𝑑𝑈 + 𝑇𝑑𝑆 − 𝑃𝑑𝑉 = −𝑑𝐺 → −𝑊=DE ≤ −∆𝐺

The decrease in Gibbs and Helmholtz energy = Work maximum done by the
system
Chapter 1. Thermodynamics

Standard molar Gibbs energies

Definition of standard Gibbs energy of reaction

∆𝐺 F = ∆𝐻 F − 𝑇∆𝑆 F

- -
∆𝐺 F = G 𝜈, ∆𝐺*,, − G 𝜈I ∆𝐺*,I
G4->8H<: 46DH<D9<:

)
where,∆𝐺&,( is standard Gibbs energies of
formation of substance i (the standard
reaction Gibbs energy of the formation of a
compound from its elements in their
reference states. The Standard Gibbs energies
of formation of the elements in their
reference state are zero.
Chapter 1. Thermodynamics

Properties of Gibbs energy

G= H-TS = U+ PV-TS
Infinitesimal changes
dG= dU+ PdV +VdP-TdS-SdT
For a closed system without additional work (W'=0): dU = TdS-PdV
dG= VdP-SdT

The variation of G with T and P

𝜕G 𝜕G
( )*= −S ( )+= V
𝜕T 𝜕P
T increases -> G decreases
P increases -> G increases
Chapter 1. Thermodynamics

Variation of Gibbs energy with temperature

𝜕𝐺
( ), = −𝑆
𝜕𝑇

G= H-TS -> S = (H-G)/T

We obtain Gibbs-Helmholtz equation:

𝜕𝐺 𝐻−G 𝜕𝐺 G H
( ), = − or ( ), − = −
𝜕𝑇 T 𝜕𝑇 T T
The variation of G with T and P

𝜕(G4T) H 𝜕(∆G4T) ∆H
=− - or =−
𝜕T * T 𝜕T * T-
Chapter 1. Thermodynamics

Variation of Gibbs energy with temperature

T2 T T
ΔG 2
ΔH 2
1
Ø ΔH=const ∫T T
d( ) = − ∫T T2 dT = −ΔH ∫T T2 dT
1 1 1

ΔGT ΔGT 1 1
2
− 1
= ΔH( − )
T2 T1 T2 T1

ΔGT ΔGT T2
f(T)
Ø ΔH=f(T) 2
− 1
= −∫ 2
dT
T2 T1 T1 T
Chapter 1. Thermodynamics

Variation of Gibbs energy with pressure

⎛ ∂G ⎞ ⎛ ∂ΔG ⎞
⎜⎝ ∂P ⎟⎠ = V ⎜⎝ ∂P ⎟⎠ = ΔV
T T

Ø Condensed systems: ΔV=0, G insignificantly affected by P

Ø For other system (ideal gas)

⎛ ∂G ⎞ RT dP
1 mol of gas ⎜⎝ ∂P ⎟⎠ = V = → dG = RT we have GP − G0 = RTlnP
T
P P

for a process ⎛ ∂ΔG ⎞

⎜⎝ ∂P ⎟⎠ = ΔV
ΔV is molar volume changes of a process/reaction
T

P2 P

ΔG − ΔG = ∫ ΔV dP
P2 P1
ΔG − ΔG = ∫ ΔV dP
P 0

P1 1
Chapter 1. Thermodynamics

Chemical potential
G, F functions for systems with variation of composition

⎛ ∂G ⎞ ⎛ ∂G ⎞ ⎛ ∂G ⎞
dG = ⎜
⎝ ∂T ⎟⎠ P,ni
dT + ⎜⎝ ⎟
∂P ⎠ T,ni
dP + ∑ ⎜⎝ ∂n ⎟⎠ dn i
i T,P,n j≠i

dG = −SdT + VdP + ∑ µ idn i

⎛ ∂G ⎞
With µi = ⎜
⎝ ∂n i ⎟⎠ T,P,n j≠i

Similarly: dF = −SdT − PdV + ∑ µ idn i

𝜕G 𝜕𝐹
µ. = ( )*,+,/!"# = ( )0,+,/!"#
𝜕n. 𝜕n.
Chapter 1. Thermodynamics

Chemical potential

𝜕G 𝜕𝐹
µ. = ( )*,+,/!"# = ( )0,+,/!"#
𝜕n. 𝜕n.
Compared to the partial molar Gibbs and Helmholtz energies

𝜕G 𝜕F
̅
𝐺. = ( )*,+,/!"# =
𝐹. = ( )*,+,/!"#
𝜕n. 𝜕n.

Chemical potential is partial molar Gibbs energy

𝜕G
;. =
𝜇. = G
𝜕n. +,*,/!"#
Chapter 1. Thermodynamics

Properties of chemical potential

Ø Chemical potential is the partial molar Gibbs energy of the substances

𝜇' = G' () JKL)

Gibbs energy of a mixture G=,E = G n' 𝜇'

Gibbs energy changes of a reaction

∆G$%&'()*+ = ' G,$*-.'( − ' G$%&'(&+( = '(n/ 𝜇/ ),$*-.'( − '(n/ 𝜇/ )$%&'(&+(

Ø Chemical potential is used for prediction of a process/reaction direction

Ø Additional work can arise from the changing of composition of a system

C
−dG = − G 𝜇' dn' = −𝛿WJ.%
Chapter 1. Thermodynamics

Properties of chemical potential

Ø Chemical potential of a gas in a gas mixture or a substance in a solution

Chemical of potential of a gas in a mixture of gas

𝜇' = 𝜇'F (T) + RTlnP'

𝜇'F 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑐ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑜𝑓 𝑖 𝑎𝑛𝑑 P' 𝑖𝑠 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

Chemical potential of a substance in a solution

𝜇' = 𝜇'F (T, P) + RTlnx'

𝜇'F 𝑖𝑠 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑐ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑜𝑓 i 𝑎𝑛𝑑 x' 𝑚𝑜𝑙𝑎𝑟 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛

THANK YOU !