2021-물리화학-Chapter 2 - 1st law of thermodynamics

Industrial Physical Chemistry
Youn Jeong Jang

Department of Chemical Engineering
Chapter 2.열역학 제 1법칙

1) 내부에너지 (Internal Energy, U)
2) 엔탈피 (Enthalpy, H)
3) 열화학 (Thermochemistry)
**Preview – 열역학 법칙
(a) 열린계, (b) 닫힌계, (c) 고립계

1. Internal Energy, U
First law of Thermodynamics : Conservation of energy (에너지 보존 법칙)

1) Total energy of isolated system is constant.
2) For closed system,
∆𝑼=𝒒+𝒘
U : Internal (total) energy of the system

(which is total K.E. and P.E. of molecules composing the system
q : Heat transferred to the system
w : Performance of work on the system
First law of Thermodynamics : Conservation of energy (에너지 보존 법칙)

3) It is impossible to invent perpetual motion machine that will produce
more energy than it takes in. (영구적으로 일할 수 있는 기관은 없다.)
∆ 𝑼 = 𝒒 + 𝒘 = (Uf – Ui ) 𝒅𝑼 = 𝒅𝒒 + 𝒅𝒘
** Perpetual motion machine : a machine that does work without consuming

fuel or some other source of energy
1-1 Work
Work is done when an object is moved against an opposing force.
𝒅𝒘 = −𝑭 𝒅𝒛
1-1 Work
Work is done when an object is moved against an opposing force.
𝒅𝒘 = −𝑭 𝒅𝒛
1-1 Work
For expansion against constant pressure
𝒅𝒘 = −𝑷𝒆𝒙𝒑 𝒅𝑽
** free expansion?
1-1 Work
For isothermal reversible expansion (assuming perfect gas)
𝒅𝒘= − 𝑷 𝒅𝑽 (at reversible expansion)

𝒏𝑹𝑻
=− 𝒅𝑽
𝑽
𝟏
= −𝒏𝑹𝑻( ) 𝒅𝑽
𝑽
1-2 Heat
Mechanism for heat transfer
1) Conduction : Solid or static fluid, molecular motion

2) Convection : Volumetric motion of fluid
3) Radiation : Electromagnetic wave emetting from that substrance
𝒅𝑼 = 𝒅𝒒 + 𝒅𝒘 = 𝒅𝒒 + 𝒅𝒘𝒆𝒙𝒑 + 𝒅𝒘𝒂𝒅𝒅
1-2 Heat
At constant volume and no additional work
𝒅𝑼 = 𝒅𝒒 + 𝒅𝒘𝒆𝒙𝒑 + 𝒅𝒘𝒂𝒅𝒅 = 𝒅𝒒𝑽
∆ 𝑼 = Uf −Ui= 𝒒𝑽
Heat transferred during Temperature change
𝒅𝒒 = 𝑪 𝒅𝑻
** where C is heat capacity

1-2 Heat
Heat capacity (C)
at constant volume and no additional work
𝒅𝑼 = 𝒅𝒒 + 𝒅𝒘𝒆𝒙𝒑 + 𝒅𝒘𝒂𝒅𝒅 = 𝒅𝒒𝑽
∆ 𝑼 = 𝒒𝑽 = 𝑪𝑽 ∆ 𝑻
𝝏𝑼
𝑪𝑽 = 𝐕 – extensive property
𝝏𝑻
𝑪𝑽, 𝒎 = 𝑪𝑽/𝒏 – intensive property
𝑪𝑽, 𝒔 = 𝑪𝑽/m – intensive property

2. Enthalpy, H
2-1 Enthalpy
In general, (assuming no additional work)
𝒅𝑼 = 𝒅𝒒 + 𝒅 𝒘𝒆𝒙𝒑
Enthalpy, H = U + pV
𝒅𝑯 = 𝒅𝑼 + 𝒑𝒅𝑽 + 𝑽𝒅𝒑
= 𝒅𝒒 + 𝒅𝒘 + 𝒑𝒅𝑽 + 𝑽𝒅𝒑
= 𝒅𝒒 + 𝑽𝒅𝒑 if dw = -pdV
𝒅𝑯 = 𝒅𝒒𝒑 if p is constant
2. Enthalpy, H
2-1 Enthalpy
Ways to measure enthalpy changes
constant-pressure flame calorimeter constant-volume bomb calorimeter

2. Enthalpy, H
2-1 Enthalpy for solid or liquid

Example; physical and chemical changes (reaction) using solid to solid materials.
It requires molar internal energy difference ∆𝑈𝑚 = 0.21 𝑘𝐽 for the transition calcite CaCO3(s)
to aragonite CaCO3(s). Calculate difference (∆𝐻𝑚 − ∆𝑈𝑚) if the transition occurred at 1 bar
where density of the calcite and aragonite was 2.71 g/mol and 2.93 g/mol, respectively.
2. Enthalpy, H
2-1 Enthalpy for perfect gas
Enthalpy, H = U + pV = U + nRT
∆𝑯𝒎 = ∆𝑼 + 𝑹𝑻∆𝒏𝒈 if perfect gas, isothermal rxn
Example; 2 mol H2 and 1 mol O2 gases do reactions following 2H2(g)+O2(g) → 2H2O(l)

Calculate difference (∆𝐻𝑚 − ∆𝑈𝑚) if the reaction is done at constant 298 K and the those
are perfect gases.
2. Enthalpy, H
2-1 Enthalpy
At constant pressure and expansion work only
𝒅𝑯 = 𝒅𝒒𝒑
Heat transferred during Temperature change
𝒅𝑯 = 𝒅𝒒𝒑 = 𝑪𝒑𝒅𝑻
** where Cp is heat capacity at constant pressure

2. Enthalpy, H
2-2 Heat capacity
𝝏𝑯 – extensive property
𝑪𝒑 = 𝐩
𝝏𝑻
𝑪𝒑, 𝒎 = 𝑪𝒑/𝒏 – intensive property
𝑪𝒑, 𝒔 = 𝑪𝒑/m
– intensive property
** where Cp is heat capacity at constant pressure
𝒄
𝑪𝒑, 𝒎 = 𝐚 + 𝐛𝐓 + 𝟐
𝑻
2. Enthalpy, H
2-2 Heat capacity

for perfect gas 𝑪𝒑 − 𝑪𝒗 = 𝐧𝐑
** Isothermal VS Adiabatic change
Isothermal process is reversible changes in volume or pressure at constant

temperature.
For isothermal process

PV = constant
𝑽𝟐 𝑷𝟏
𝐪 = 𝒏𝑹𝑻𝒍𝒏 = 𝒏𝑹𝑻𝒍𝒏
𝑽𝟏 𝑷𝟐
Adiabatic expansion is reversible changes in volume, temperature, and pressure

without exchange of heat, q.
∆𝐔 = 𝑻𝒇 − 𝑻𝒊 𝑪𝑽 = 𝑪𝑽 ∆𝐓
𝒅𝑼 = 𝑪𝑽 𝒅𝑻 = −𝒑𝒅𝑽

∆𝐔 = 𝑻𝒇 − 𝑻𝒊 𝑪𝑽 = 𝑪𝑽 ∆𝐓
𝒅𝑼 = 𝑪𝑽 𝒅𝑻 = −𝒑𝒅𝑽
𝑻𝒇 𝑽𝒊 𝑽𝒊 𝑻𝑪𝒊 = 𝑽𝒇 𝑻𝑪𝒇
𝑪𝑽 𝒍𝒏 = −𝒏𝑹𝒍𝒏
𝑻𝒊 𝑽𝒇
Where C = 𝐶𝑉,𝑚 /𝑅

𝑻𝒊 𝑷𝒊 𝑽 𝒊 𝑽𝒇 1/𝑐
= =
𝑻𝒇 𝑷𝒇 𝑽 𝒇 𝑽𝒊
𝑟
𝒑𝒊 𝑽𝒊
=1 Where 𝛾 = 𝐶𝑝,𝑚 /𝐶𝑉,𝑚 𝑷𝒊 𝑽𝒓𝒊 = 𝑷𝒇 𝑽𝒓𝒇
𝒑𝒇 𝑽𝒇
3. Thermochemistry – Heat of reaction
A+B→C+D
The study of heat effect related with

: Chemical reaction, Formation of solution, Phase transition, etc
Exothermic or Endothermic reaction
: Exothermic Rxn : ∆Hsys < 0 (𝑞𝑝 <0)
: Endothermic Rxn : ∆Hsys > 0 (𝑞𝑝 >0)

3-1 standard enthalpy change, ∆𝑯𝜽
Enthalpy is a state function.

Thus, the change in enthalpy is independent of the path of change.
It represents that the enthalpy change for any reaction can be calculated
from a suitable combination of values for standard reference reactions.
** standard enthalpy of formation ∆𝒇 𝑯𝜽

: Reaction enthalpy for the formation of compound from its elements in
their reference states (1 bar).
: Conventionally, heat of formation of elements is zero.
: Heat of reaction : standard reaction enthalpy
∆𝒓 𝑯𝜽 = ෍ 𝝂∆𝒇 𝑯𝜽 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − ෍ 𝝂∆𝒇 𝑯𝜽 (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔)
Where 𝜈 is stoichiometric coefficient

aA + bB → cC + dD
∆𝒓 𝑯𝜽 = ෍ 𝝂∆𝒇 𝑯𝜽 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − ෍ 𝝂∆𝒇 𝑯𝜽 (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔)

3-2 Hess’ law
- The standard enthalpy of an overall reaction is the sum of the

standard enthalpies of the individual reactions into which a reaction
may be divided.
∆𝒓 𝑯𝜽 𝑨 → 𝑪 = ∆𝒓 𝑯𝜽 𝑨 → 𝑩 + ∆𝒓 𝑯𝜽 (𝑩 → 𝑪)
3-2 Hess’ law
Example. Calculate standard enthalpy of reaction for propene

combustion using values of standard enthalpies for reaction for the
following reactions.
𝑪𝑯𝟐 = 𝑪𝑯 − 𝑪𝑯𝟑 + 𝑯𝟐 → 𝑪𝑯𝟑 − 𝑪𝑯𝟐 − 𝑪𝑯𝟑 ∆ 𝒓 𝑯𝜽 = −𝟏𝟐𝟒 𝑲𝑱/𝒎𝒐𝒍

𝑪𝑯𝟑𝑪𝑯𝟐𝑪𝑯𝟑 + 𝟓𝑶𝟐 → 𝟑𝑪𝑶𝟐 + 𝟒𝑯𝟐𝑶 ∆ 𝒓 𝑯𝜽 = −𝟐𝟐𝟐𝟎 𝑲𝑱/𝒎𝒐𝒍
𝟏/𝟐𝑶𝟐 + 𝑯𝟐 → 𝑯𝟐𝑶 ∆ 𝒓 𝑯𝜽 = −𝟐𝟖𝟔𝑲𝑱/𝒎𝒐𝒍
3-3 Kirchhoff’s law – Temp. dependent ∆ 𝒓 𝑯𝜽
At constant pressure, enthalpy is temperature dependent.
𝒅𝑯 = 𝒅𝒒𝒑 = 𝑪𝒑𝒅𝑻
𝑻𝟐
𝑯(𝑻𝟐 ) = 𝑯(𝑻𝟏 ) + න 𝑪𝒑𝒅𝑻
𝑻𝟏
𝑻𝟐
∆𝒓 𝑯𝜽 𝑻𝟐 = ∆𝒓 𝑯𝜽 𝑻𝟏 + න ∆𝒓 𝑪𝜽𝒑 𝒅𝑻
𝑻𝟏
Where, ∆𝒓 𝑪𝜽𝒑 = σ 𝝂∆𝑪𝜽𝒑,𝒎 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − σ 𝝂∆𝑪𝜽𝒑,𝒎 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕
3-3 Kirchhoff’s law
Example. Calculate standard enthalpy for reaction at 100℃ using the

values followed.
2H2(g) + O2(g) → 2H2O(g)
∆𝒓 𝑯𝜽 𝟐𝟗𝟖𝑲 = -241.82kJ/mol
𝑪𝜽𝒑,𝒎 𝑯𝟐, 𝒈 = 𝟐𝟖. 𝟖𝟒 𝑱/𝑲𝒎𝒐𝒍 𝑪𝜽𝒑,𝒎 𝑶𝟐, 𝒈 = 𝟐𝟗. 𝟑𝟕 𝑱/𝑲𝒎𝒐𝒍 𝑪𝜽𝒑,𝒎 𝑯𝟐𝑶, 𝒈 = 𝟑𝟑. 𝟓𝟖 𝑱/𝑲𝒎𝒐𝒍

2021-물리화학-Chapter 2 - 1st law of thermodynamics

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Industrial Physical Chemistry

Youn Jeong Jang

Chapter 2.열역학 제 1법칙

(a) 열린계, (b) 닫힌계, (c) 고립계

First law of Thermodynamics : Conservation of energy (에너지 보존 법칙)

U : Internal (total) energy of the system

First law of Thermodynamics : Conservation of energy (에너지 보존 법칙)

** Perpetual motion machine : a machine that does work without consuming

For expansion against constant pressure

For isothermal reversible expansion (assuming perfect gas)

𝒅𝒘= − 𝑷 𝒅𝑽 (at reversible expansion)

Mechanism for heat transfer

1) Conduction : Solid or static fluid, molecular motion

At constant volume and no additional work

𝒅𝑼 = 𝒅𝒒 + 𝒅𝒘𝒆𝒙𝒑 + 𝒅𝒘𝒂𝒅𝒅 = 𝒅𝒒𝑽

Heat transferred during Temperature change

** where C is heat capacity

Heat capacity (C)

at constant volume and no additional work

𝒅𝑼 = 𝒅𝒒 + 𝒅𝒘𝒆𝒙𝒑 + 𝒅𝒘𝒂𝒅𝒅 = 𝒅𝒒𝑽

𝑪𝑽, 𝒎 = 𝑪𝑽/𝒏 – intensive property

𝑪𝑽, 𝒔 = 𝑪𝑽/m – intensive property

In general, (assuming no additional work)

Ways to measure enthalpy changes

constant-pressure flame calorimeter constant-volume bomb calorimeter

2-1 Enthalpy for solid or liquid

2-1 Enthalpy for perfect gas

∆𝑯𝒎 = ∆𝑼 + 𝑹𝑻∆𝒏𝒈 if perfect gas, isothermal rxn

Example; 2 mol H2 and 1 mol O2 gases do reactions following 2H2(g)+O2(g) → 2H2O(l)

At constant pressure and expansion work only

Heat transferred during Temperature change

** where Cp is heat capacity at constant pressure

2-2 Heat capacity

𝑪𝒑, 𝒎 = 𝑪𝒑/𝒏 – intensive property

** where Cp is heat capacity at constant pressure

2-2 Heat capacity

Isothermal process is reversible changes in volume or pressure at constant

For isothermal process

Adiabatic expansion is reversible changes in volume, temperature, and pressure

Adiabatic expansion is reversible changes in volume, temperature, and pressure

Adiabatic expansion is reversible changes in volume, temperature, and pressure

The study of heat effect related with

Exothermic or Endothermic reaction

: Exothermic Rxn : ∆Hsys < 0 (𝑞𝑝 <0)

: Endothermic Rxn : ∆Hsys > 0 (𝑞𝑝 >0)

3-1 standard enthalpy change, ∆𝑯𝜽

Enthalpy is a state function.

3-1 standard enthalpy change, ∆𝑯𝜽

** standard enthalpy of formation ∆𝒇 𝑯𝜽

∆𝒓 𝑯𝜽 = ෍ 𝝂∆𝒇 𝑯𝜽 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − ෍ 𝝂∆𝒇 𝑯𝜽 (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔)

Where 𝜈 is stoichiometric coefficient

3-1 standard enthalpy change, ∆𝑯𝜽

∆𝒓 𝑯𝜽 = ෍ 𝝂∆𝒇 𝑯𝜽 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − ෍ 𝝂∆𝒇 𝑯𝜽 (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔)

3-2 Hess’ law

- The standard enthalpy of an overall reaction is the sum of the

3-2 Hess’ law

Example. Calculate standard enthalpy of reaction for propene

𝑪𝑯𝟐 = 𝑪𝑯 − 𝑪𝑯𝟑 + 𝑯𝟐 → 𝑪𝑯𝟑 − 𝑪𝑯𝟐 − 𝑪𝑯𝟑 ∆ 𝒓 𝑯𝜽 = −𝟏𝟐𝟒 𝑲𝑱/𝒎𝒐𝒍

3-3 Kirchhoff’s law – Temp. dependent ∆ 𝒓 𝑯𝜽