Chapter 1 𝑑𝐺 ′ = −𝑆 ′ 𝑑𝑇 + 𝑉 ′ 𝑑𝑃 + ∑ 𝐺̅𝑖 𝑑𝑛𝑖 ; 𝐺̅𝑖 = 𝜇𝑖

𝜕𝑄 𝜕𝑄
Δ𝑈 = 𝑄 + 𝑊, 𝐶𝑃 = ( 𝜕𝑇 ) , 𝐶𝑉 = ( 𝜕𝑇 ) , 𝛼 =
𝑃 𝑉 1st and 2nd consequence:
1 𝜕𝑉 1 𝜕𝑉 𝐶 𝐶
(𝜕𝑇 ) , 𝛽 = 𝑉 (𝜕𝑃 ) , 𝑊 = −𝑃Δ𝑉; ′
𝑑𝑉𝑇,𝑃 =∑ 𝑉̅𝑘 𝑑𝑛𝑘 𝑉′ = ∑ 𝑉̅𝑘 𝑛𝑘
𝑉 𝑃 𝑇
𝑐 𝑘=1 𝑘=1
𝐶𝑃 = 𝑎 + 𝑏𝑇 + 2
𝑇
3rd consequence: Gibbs-Duhem
𝐶
Chapter 2: Law of thermodynamic 𝑑𝐵′
𝐶 ∑ 𝑛𝑘 𝑑𝐵̅𝑘 = 0
First law: The first law of thermodynamics is simply, =∑ [𝐵̅𝑘 𝑑𝑛𝑘 + 𝑛𝑘 𝑑𝐵̅𝑘 ] 𝑘=1
the principle of conservation of energy; that is energy 𝑘=1 Activity of k
can be neither created nor destroyed. 𝐺𝐴̅ 𝑜 = 𝜇𝐴𝑜 and so
𝑑𝑈 = 𝑄 + 𝑊 + 𝑊′ and for an infinitesimal changes Molar quantities 𝑑Δ𝐺̅𝑚𝑖𝑥
in the condition of the system, 𝑑𝑈 = 𝛿𝑄 + 𝛿𝑊 + 𝐵′ 𝜇𝐴 − 𝜇̅ 𝐴𝑜 = Δ𝜇𝑘 = Δ𝐺̅𝑚𝑖𝑥 − 𝑋𝐵 = 𝑅𝑇 ln 𝑎𝑘
𝐵̅ = Different from 𝐵̅𝑘 𝑑𝑋𝐵
𝛿𝑊′ 𝑛𝑡𝑜𝑡
𝑐 𝜇̅ 𝑘𝑜 is the chemical potential of k in its reference state
𝑑𝐵 ′ ∑𝑐𝑘=1 𝐵̅𝑘 𝑑𝑛𝑘 𝑎𝑘 is the activity of k in its reference state.
The second law of thermodynamics states that for a 𝑑𝐵̅ = = = ∑ 𝐵̅𝑘 𝑑𝑋𝑘
𝑛𝑡𝑜𝑡 𝑛𝑡𝑜𝑡 When 𝜇𝑘 = 𝜇̅ 𝑘𝑜 , 𝑎𝑘 = 1, Pure material
𝑘=1
system, the intensive thermodynamic quantities such 𝑐 𝑐 When 𝑎𝑘 = 𝑋𝑘 , 𝛾𝑘 = 1 (Ideal solution)
as temperature, pressure, and chemical potential Thus, 𝐵̅ = ∑ 𝑋𝑘 𝐵̅𝑘 ̅ = ∑ 𝑛𝑘 𝐵̅𝑘
and 𝐵′
tend to become more uniform as time goes by, 𝑘=1 𝑘=1 Ideal solution
unless there is an outside influence which works to Partial molal property Total property
maintain the differences. Entropy, S, always changes Relation between partial molal properties and total Δ𝐺𝑘̅ = 𝑅𝑇 ln 𝑋𝑘 Δ𝐺𝑚𝑖𝑥 = 𝑅𝑇 ∑𝑐𝑘=1 𝑋𝑘 ln 𝑋𝑘
in the same direction. By convention, S always properties (in terms of mole fraction). Δ𝑆𝑘̅ = −𝑅 ln 𝑋𝑘 Δ𝑆𝑚𝑖𝑥 = −𝑅 ∑𝑐𝑘=1 𝑋𝑘 ln 𝑋𝑘
Δ𝑉̅𝑘 = 0 Δ𝑉𝑚𝑖𝑥 = 0
increases. Starting from 𝐵̅ = 𝐵̅𝐴 𝑋𝐴 + 𝐵̅𝐵 𝑋𝐵 ̅𝑘 = 0
′ Δ𝐻 Δ𝐻𝑚𝑖𝑥 = 0
Δ𝑆𝑠𝑢𝑚 = (Δ𝑆𝑡 + Δ𝑆𝑝𝑟𝑜𝑑 ) + (Δ𝑆𝑡′ + Δ𝑆𝑝𝑟𝑜𝑑 ) 𝑑𝐵̅
And 𝑑𝑋 = 𝐵̅𝐵 − 𝐵̅𝐴, rearrange and bring 𝐵̅𝐴 to LHS ̅𝑘 = 0
Δ𝑈 Δ𝑈𝑚𝑖𝑥 = 0
= Δ𝑆𝑝𝑟𝑜𝑑 + Δ𝑆𝑝𝑟𝑜𝑑 ′ 𝐵
Sub into first equation and rearrange to make 𝐵̅𝐴 to
LHS again to give Real solution
To relate entropy with energy in a closed system, Δ𝑆𝑘̅ = −𝑅𝑙𝑛𝑋𝑘 (same as ideal solution)
𝛿𝑄𝑟𝑒𝑣 𝐶𝑃 𝐶𝑉 𝑑𝐵̅ 𝑑𝐵̅
𝑑𝑆 = = or 𝑉̅𝐴 = 𝑉̅ + (1 − 𝑋𝐴 ) = 𝑉̅ − 𝑋𝐵 Δ𝐻𝑘 = Δ𝐻 ̅𝑘 (𝑋1 , 𝑋2 , … )
𝑇 𝑇 𝑇 𝑑𝑋𝐴 𝑑𝑋𝐵
Simplest real solution’s heat of mixing:
𝑑𝐺̅ 𝑑𝐺̅
𝜇𝐴 = 𝐺̅ + (1 − 𝑋𝐴 ) = 𝐺̅ − 𝑋𝐵 Δ𝐻𝑚𝑖𝑥 = 𝑎𝑋1 𝑋2 , thus
Remarks about entropy 𝑑𝑋𝐴 𝑑𝑋𝐵 Δ𝐺𝑚𝑖𝑥 = 𝑎𝑋1 𝑋2 + 𝑅𝑇(𝑋1 ln 𝑋1 + 𝑋2 ln 𝑋2 )
1. Process can occur in a certain direction only, not in
any direction. Prove that 𝐺̅ = 𝜇𝐴 𝑋𝐴 + 𝜇𝐵 𝑋𝐵 = ∑𝜇𝑘 𝑋𝑘 Basically for real solution, Δ𝐻𝑚𝑖𝑥 = 𝑓(𝑋𝐴 𝑋𝐵 ) is
2. Entropy is a non-conserved property. Multiply 𝜇𝐴 and 𝜇𝐵 by 𝑋𝐴 and 𝑋𝐵 respectively. Add usually given. Δ𝑆𝑚𝑖𝑥 can follow ideal solution. And
3. The performance of the engineering system is 𝜇𝐴 𝑋𝐴 + 𝜇𝐵 and then simply the equation. Δ𝐺𝑚𝑖𝑥 = Δ𝐻𝑚𝑖𝑥 − 𝑇Δ𝑆𝑚𝑖𝑥
degraded by the presence of irreversibility, and
entropy generation is a measure of the magnitude of Graphical intepretation Chapter 5: Phase Disgram
the irreversibilities present during the process. 𝑑𝐺̅
From 𝜇𝐴 = 𝐺̅ − 𝑋𝐵 (𝑑𝑋 ), rearrange and make 𝐺̅ as In a P-T phase diagram, the phase boundary follows
𝐵
the LHS, clausius-clapeyron equation.
Combining first and second law gives dU = TdS -PdV 𝑑𝐺̅ 𝑑𝑃 𝑆𝛽 − 𝑆 𝛼 Δ𝑆
𝐺̅ = 𝜇𝐴 + 𝑋𝐵 (𝑑𝑋 ), and this is the quation of 𝐺 − 𝑋𝐵 ( )= 𝛽 =
𝐵 𝑑𝑇 𝑉 − 𝑉 𝛼 Δ𝑉
Chapter 3: Thermodynamic variables and relations curve. At different 𝑋𝐵 , 𝐺̅ will be different because 𝜇𝐴
is a function of X too. •A eutectic system is a mixture of chemical
Basic Energy function But in simplicity, 𝜇𝐴 is the y-intersect for gradient at compounds or elements that has a single chemical
H = U + PV G = U + PV -TS 𝑋𝐵 . composition that solidifies at a lower temperature
dU = TdS -PdV dH = TdS + VdP than any other composition. This composition is
dG = -SdT + VdP known as the eutectic composition and the
temperature is known as the eutectic temperature.
Coefficient relations, La+b
For a general function, 𝑍 = 𝑍(𝑋, 𝑌), 𝑑𝑍 = 𝑀𝑑𝑋 +
𝑁𝑑𝑌. And 𝑀 = (𝜕𝑍/𝜕𝑋)Y and 𝑁 = (𝜕𝑍/𝜕𝑌)X Equibrium condition
𝛽 𝛽
𝑑𝐺 ′ = 0; 𝜇𝐴𝛼 = 𝜇𝐴 = 𝜇𝐴𝛾 = ⋯ = 𝜇𝐵𝛼 = 𝜇𝐵 = 𝜇𝐵𝛾
Maxwell relations:
∑𝑑𝑛𝑘𝛼 = 0 for the k compenent in all phases
𝜕𝑃 𝜕𝑇 𝜕𝑇 𝜕𝑉
−( ) = ( ) ( ) =( )
𝜕𝑆 𝑉 𝜕𝑉 𝑆 𝜕𝑃 𝑆 𝜕𝑆 𝑃
Lever Rule:
𝜕𝑆 𝜕𝑉 𝛽 𝛽
−( ) = ( ) 𝑓𝛼 = (𝑋𝐵 − 𝑋𝐵 )/(𝑋𝐵 − 𝑋𝐵𝛼 )
𝜕𝑃 𝑇 𝜕𝑇 𝑃
For the solid phase ΔHmix> 0, i.e. the A and B atoms
‘dislike’ each other. •The effect of a positive ΔHmixin
Now we can convert basic energy function into in
the solid also results into a minimum melting point of
terms of dP and dT, for easier calculation.
𝑑𝑉 = 𝑉𝛼𝑑𝑇 − 𝑉𝛽𝑑𝑃 the mixture. The atoms in the alloy ‘repel’ each other
𝐶𝑝 making the disruption of the solid into a liquid phase
𝑑𝑆 = 𝑑𝑇 − 𝑉𝛼𝑑𝑃 possible at lower temperatures than in either pure A
𝑇
𝑑𝑈 = (𝐶𝑝 − 𝑃𝑉𝛼)𝑑𝑇 + 𝑉(𝑃𝛽 − 𝑇𝛼)𝑑𝑃 or pure B.
𝑑𝐻 = 𝐶𝑝 𝑑𝑇 + 𝑉(1 − 𝑇𝛼)𝑑𝑃 If ΔHmixsis much larger than zero, the miscibility gap
𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 can extend into the liquid phase, giving rise to a
simple eutectic phase diagram.
Conditions for equilibrium
For an isolated system, δQ = 0. Thus its entropy can
only increase. As a result, they will be in equilibrium 𝑉̅ (𝑋𝐵 ) is the 𝑉̅ when 𝑋 = 𝑋𝐵
when their entropy is maximal. i.e. dS=dG=dT=dP=0
Mixing process
Clausius-Clapeyron equation Δ𝑉̅𝑚𝑖𝑥 = 𝑉̅ (𝑋𝐵 ) − (𝑋𝐴 𝑉̅𝐴0 + 𝑋𝐵 𝑉̅𝐵0 )
𝑑𝑃 Δ𝑆 Δ𝐻 Δ𝑉̅𝑚𝑖𝑥 = (𝑋𝐴 𝑉̅𝐴 + 𝑋𝐵 𝑉̅𝐵 ) − (𝑋𝐴 𝑉̅𝐴0 + 𝑋𝐵 𝑉̅𝐵0 )
( )= =
𝑑𝑇 Δ𝑉 𝑇Δ𝑉
= ∑ 𝑋𝑘 Δ𝑉̅𝑘
𝑘
For Ideal gas
̅𝑚𝑖𝑥 = 𝐻
Δ𝐻 ̅ (𝑋𝐵 ) − (𝑋𝐴 𝐻
̅𝐴0 + 𝑋𝐵 𝐻
̅𝐵0 ) = ∑ 𝑋𝑘 Δ𝐻
̅𝑘
𝑑𝑈 = 𝐶𝑉 𝑑𝑇 and 𝑑𝐻 = 𝐶𝑃 𝑑𝑇 𝑘
1 𝜕𝑉 𝑃 𝜕 𝑛𝑅𝑇 𝑃 𝑛𝑅 Δ𝐺̅𝑚𝑖𝑥 = 𝐺̅ (𝑋𝐵 ) − (𝑋𝐴 𝐺𝐴̅ 0 + 𝑋𝐵 𝐺̅𝐵0 ) = ∑ 𝑋𝑘 Δ𝐺̅𝑘
𝛼= ( ) = [ ( )] = ( )( )
𝑉 𝜕𝑇 𝑃 𝑛𝑅𝑇 𝜕𝑃 𝑃 𝑃 𝑛𝑅𝑇 𝑃 𝑘
1
= Δ𝐻̅𝑚𝑖𝑥 is equal to the heat exchange wit environment
𝑇
1 𝜕𝑉 𝑃 𝜕 𝑛𝑅𝑇 upon mixing a total one mole of pure component A
𝛽=− ( ) =− [ ( )] ̅𝑚𝑖𝑥 is
𝑉 𝜕𝑃 𝑇 𝑛𝑅𝑇 𝜕𝑃 𝑃 𝑇 and B. At concentration of 𝑋𝐵 , when Δ𝐻
𝑃 𝑛𝑅𝑇 1 negative, it is exothermic, vice versa.
=− (− 2 ) =
𝑛𝑅𝑇 𝑃 𝑃

Chapter 4: Solutions
Molar fraction: 𝑋𝑖 = 𝑛𝑖 /𝑛𝑡𝑜𝑡 with 𝑛𝑡𝑜𝑡 = ∑𝑛𝑖
Atomic percentage, at% = 100%𝑋𝑖
Weight percentage, 𝑤𝑖 = 𝑊𝑖 /𝑊𝑡𝑜𝑡 with 𝑊𝑡𝑜𝑡 = ∑𝑊𝑖
Concentration, 𝐶𝑖 = 𝑛𝑖 /𝑉 or sometimes 𝐶𝑖 = 𝑊𝑖 /𝑉
Excess volume, Δ𝑉𝑒𝑥𝑐𝑒𝑠𝑠 = 𝑉𝑠𝑜𝑙 − (𝑉𝑒𝑡ℎ𝑎𝑛𝑜𝑙 + 𝑉𝑤𝑎𝑡𝑒𝑟 )
and 𝑉𝑠𝑜𝑙 < 𝑉𝑒𝑡ℎ𝑎𝑛𝑜𝑙 + 𝑉𝑤𝑎𝑡𝑒𝑟 The value of Δ𝐺̅𝑚𝑖𝑥 is an important quantity as its
Volume of solution, 𝑉 ′ = 𝑉′(𝑇, 𝑃, 𝑛1 , 𝑛2 , … , 𝑛𝐶 ) sign determines whether a mixing will occur or not. A
′ 𝜕𝑉 ′ 𝜕𝑉 ′
Differential 𝑑𝑉 = ( 𝜕𝑇 ) 𝑑𝑇 + ( 𝜕𝑃 ) 𝑑𝑃 + ̅
negative Δ𝐺𝑚𝑖𝑥 means that there’s a thermodynamic Eutectic: L A + B; Peritectic: L+A  B
𝜕𝑉 ′ driving force for mixing and pure components will
∑ (𝜕𝑛 ) 𝑑𝑛𝑘
𝑘 spontaneously form a solution upon contact. When For mixture of ideal gases, derive the following
Partial Molal properties: Δ𝐺̅𝑚𝑖𝑥 is positive, both components are immisible,
𝜕𝑉 ′ 𝜕𝑉 ′ Δ𝑉̅𝑚𝑖𝑥 = Δ𝐻̅𝑚𝑖𝑥 = Δ𝑈 ̅𝑚𝑖𝑥 = 0
And (𝜕𝑛 ) 𝑑𝑛𝑘 can be simplified as 𝑉̅𝑘 = (𝜕𝑛 ), and and they form 2 phase dispersion of pure A phase For I. G, Δ𝜇𝑘 = μk − 𝜇𝑘𝑜 = Δ𝐺̅𝑘 = 𝑅𝑇 ln 𝑋𝑘
𝑘 𝑘
mixed with pure B phase. 𝑑Δ𝜇𝑘
for 𝐺̅𝑘 , it’s 𝜇𝑘 Since 𝑑𝜇𝑘 = −𝑆𝑘̅ 𝑑𝑇 + 𝑉̅𝑘 𝑑𝑃, Δ𝑉̅𝑘 = ( ) =0
Intensive property: A property of a system is 𝑑𝑃 𝑇
intensiveit may be defined to have a value at a point 𝐻𝑒𝑛𝑐𝑒, Δ𝑉̅𝑘 = 0. Δ𝑉̅𝑚𝑖𝑥 = ∑ 𝑋𝑘 Δ𝑉̅𝑘 = 0
in the system. E.g. Temp, Pressure, Density ̅𝑘 = Δ𝐺̅𝑘 + 𝑇Δ𝑆𝑘̅ = 0
Δ𝐻
A property of a system is extensive if it is the system ̅𝑘 = Δ𝐻
̅𝑘 − 𝑃Δ𝑉̅𝑘 − 𝑉𝑘 Δ𝑃 = 0
Δ𝑈
as whole. E.g. Volume, Weight, H, G
Unit of J=Pa.m3
For solution,
∫ ln 𝑥 𝑑𝑥 = 𝑥𝑙𝑛(𝑥) − 𝑥 + 𝐶
𝑑𝑉 ′ = 𝛼𝑉 ′ 𝑑𝑇 − 𝛽𝑉 ′ 𝑑𝑃 + ∑ 𝑉̅𝑖 𝑑𝑛𝑖 Graphical of Δ𝐺𝑚𝑖𝑥 ∫(1 /𝑥 2 )𝑑𝑥 = −1/𝑥 + 𝐶f