Thermodynamics

Ashok Kumar Dasmahapatra

Department of Chemical Engineering, Indian Institute of Technology Guwahati

Heat Effects
Heat Effects

 Sensible Heat Effects – Temperature Dependence of Heat

Capacity, Sensible Heat Integral

 Latent Heat of Pure Substances

 Standard Heat of Reaction

 Standard Heat of Formation

 Standard Heat of Combustion

 Temperature Dependence of DH°

Heat Effects
Sensible Heat Effects – Temperature Dependence of Heat Capacity,
Sensible Heat Integral
 Chemical reaction – involve heat transfer
 Certain chemical reaction happens only at a particular temperature (sometimes, at a
particular pressure also)
 Heat transfer – either add to the reactor or remove from the reactor
 Sensible heat – temperature change
 Latent heat – phase change

Sensible Heat Effects

 The transferred heat causes only change in temperature, no phase change, no

reaction, no change in composition, etc.
 We have already learnt that internal energy is a function of two state variables (e.g.,
T, V)
𝑈 = 𝑈(𝑇, 𝑉) 𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉
𝜕𝑇 𝑉
𝜕𝑉 𝑇 0, for a constant volume process;
𝜕𝑈 U is independent of V, ideal gas,
𝑑𝑈 = 𝐶𝑉 𝑑𝑇 + 𝑑𝑉
𝜕𝑉 𝑇 incompressible fluids
Heat Effects
Sensible Heat Effects – Temperature Dependence of Heat Capacity,
Sensible Heat Integral

𝑑𝑈 = 𝐶𝑉 𝑑𝑇 → ∆𝑈 = 𝐶𝑉 𝑑𝑇 … … … … . . (1)

For a mechanically reversible constant V process, 𝑄 = ∆𝑈 If 𝐶𝑃 and 𝐶𝑉  constant

𝑇2
∆𝑼 = 𝑪𝑽 𝑻𝟐 − 𝑻𝟏
𝑄 = ∆𝑈 = 𝐶𝑉 𝑑𝑇
𝑇1 ∆𝑯 = 𝑪𝑷 𝑻𝟐 − 𝑻𝟏

For enthalpy, H:
0, for a constant pressure process;
𝜕𝐻 𝜕𝑈
𝐻 = 𝑈(𝑇, 𝑃) 𝑑𝐻 = 𝑑𝑇 + 𝑑𝑃 H is independent of P, ideal gas,
𝜕𝑇 𝑃 𝜕𝑃 𝑇 low pressure

𝑑𝐻 = 𝐶𝑃 𝑑𝑇 → ∆𝐻 = 𝐶𝑃 𝑑𝑇 … … … … . . (2)

For a mechanically reversible constant P process, 𝑄 = ∆𝐻 Q = ∆𝐻 = 𝐶𝑃 𝑑𝑇 … … (3)

Heat Effects
Temperature Dependence of Heat Capacity
Temperature dependency of heat capacity is given by an empirical expression:

𝑪𝑷 𝑪𝑷
= 𝜶 + 𝜷𝑻 + 𝜸𝑻𝟐 𝒂𝒏𝒅 = 𝒂 + 𝒃𝑻 + 𝒄𝑻−𝟐
𝑹 𝑹
𝜶 , 𝜷, 𝜸, 𝒂 , 𝒃 and 𝒄 are constant, and represents characteristics properties of
a substance
𝑪𝑷 𝑨 and 𝑩 contribute
A combined expression: = 𝑨 + 𝑩𝑻 + 𝑪𝑻𝟐 + 𝑫𝑻−𝟐 ……..(4) more towards CP
𝑹

𝒊𝒈
𝑪𝑷
For ideal gas: = 𝑨 + 𝑩𝑻 + 𝑪𝑻𝟐 + 𝑫𝑻−𝟐 ….. (5)
𝑹
𝒊𝒈 𝒊𝒈
𝑪𝑽
=
𝑪𝑷
− 𝟏 …… (6)  Temperature dependency
Relation between 𝑪𝑷 and 𝑪𝑽 : 𝑹 𝑹 is same for 𝑪𝑷 and 𝑪𝑽 :

Ideal 𝑪𝑷 and 𝑪𝑽 may be used for real gases, only at P 0

Heat Effects
Temperature Dependence of Heat Capacity
For Gas Mixture:

𝒊𝒈 𝒊𝒈 𝒊𝒈 𝒊𝒈
𝑪𝑷𝒎𝒊𝒙𝒕𝒖𝒓𝒆 = 𝒚𝑨 𝑪𝑷𝑨 + 𝒚𝑩 𝑪𝑷𝑩 + 𝒚𝑪 𝑪𝑷𝑪 …….. (7)
𝒊𝒈 𝒊𝒈 𝒊𝒈
𝑪𝑷𝑨 , 𝑪𝑷𝑩 , 𝑪𝑷𝑪  molar heat capacities of pure A, B and C
𝒚𝑨 , 𝒚𝑩 , 𝒚𝑪  mole fraction of A, B and C

Evaluation of Sensible Heat Integral

To evaluate the integral 𝐶𝑃𝑑𝑇 we use the expression of 𝐶𝑃 as a function of 𝑇

𝑻 𝑪𝑷 𝑩 𝑪 𝑫 𝝉−𝟏
𝑻𝟎 𝑹
𝒅𝑻 = 𝑨𝑻𝟎 𝝉 − 𝟏 + 𝟐 𝑻𝟐𝟎 𝝉𝟐 − 𝟏 + 𝟑 𝑻𝟑𝟎 𝝉𝟑 − 𝟏 + 𝑻 ……. (8)
𝟎 𝝉
𝑇
where, 𝜏 = 𝑇
0
Heat Effects
Evaluation of Sensible Heat Integral

𝑻 𝑪𝑷 𝑩 𝑪 𝑫 𝝉−𝟏
𝑻𝟎 𝑹
𝒅𝑻 = 𝑨𝑻𝟎 𝝉 − 𝟏 + 𝟐 𝑻𝟐𝟎 𝝉𝟐 − 𝟏 + 𝟑 𝑻𝟑𝟎 𝝉𝟑 − 𝟏 + 𝑻 ……. (8)
𝟎 𝝉

𝑇
where, 𝜏 ≡ 𝑇
0

Given the values of 𝑻𝟎 and 𝑻 along with the constants, Q or DH can easily be estimated.

Special case: Estimate 𝑻, given 𝑻𝟎 , 𝑸 and ∆𝑯  Iterative method

Re-write eq. (8):

𝑻
𝑪𝑷 𝑩 𝟐 𝑪 𝟑 𝟐 𝑫 𝝉−𝟏
𝒅𝑻 = 𝑨𝑻𝟎 𝝉 − 𝟏 + 𝑻𝟎 𝝉 − 𝟏 𝝉 + 𝟏 + 𝑻𝟎 𝝉 + 𝝉 + 𝟏 𝝉 − 𝟏 +
𝑻𝟎 𝑹 𝟐 𝟑 𝑻𝟎 𝝉

Re-arrange:
𝑻
𝑪𝑷 𝑩 𝑪 𝑫
𝒅𝑻 = 𝑨𝑻𝟎 + 𝑻𝟐𝟎 𝝉 + 𝟏 + 𝑻𝟑𝟎 𝝉𝟐 + 𝝉 + 𝟏 + 𝝉 − 𝟏 … … . . (𝟗)
𝑻𝟎 𝑹 𝟐 𝟑 𝝉𝑻𝟎
Heat Effects
Evaluation of Sensible Heat Integral
Re-arrange:
𝑻
𝑪𝑷 𝑩 𝑪 𝑫
𝒅𝑻 = 𝑨𝑻𝟎 + 𝑻𝟐𝟎 𝝉 + 𝟏 + 𝑻𝟑𝟎 𝝉𝟐 + 𝝉 + 𝟏 + 𝝉 − 𝟏 … … . . (𝟗)
𝑻𝟎 𝑹 𝟐 𝟑 𝝉𝑻𝟎
𝑻−𝑻𝟎
Since, 𝝉 − 𝟏 = 𝑻𝟎

𝑻
𝑪𝑷 𝑩 𝑪 𝑫 𝑻 − 𝑻𝟎
𝒅𝑻 = 𝑨𝑻𝟎 + 𝑻𝟐𝟎 𝝉 + 𝟏 + 𝑻𝟑𝟎 𝝉𝟐 + 𝝉 + 𝟏 + … … . . (𝟏𝟎)
𝑻𝟎 𝑹 𝟐 𝟑 𝝉𝑻𝟎 𝑻𝟎

𝑻
𝑪𝑷 𝑩 𝑪 𝑫
𝒅𝑻 = 𝑨 + 𝑻𝟎 𝝉 + 𝟏 + 𝑻𝟐𝟎 𝝉𝟐 + 𝝉 + 𝟏 + 𝟐 (𝑻 − 𝑻𝟎 ) … … . . (𝟏𝟎)
𝑻𝟎 𝑹 𝟐 𝟑 𝝉𝑻 𝟎

𝑪𝑷 H
Heat Effects
Evaluation of Sensible Heat Integral

𝑻
𝑪𝑷 𝑩 𝑪 𝑫
𝒅𝑻 = 𝑨 + 𝑻𝟎 𝝉 + 𝟏 + 𝑻𝟐𝟎 𝝉𝟐 + 𝝉 + 𝟏 + 𝟐 (𝑻 − 𝑻𝟎 ) … … . . (𝟏𝟎)
𝑻𝟎 𝑹 𝟐 𝟑 𝝉𝑻 𝟎

𝑪𝑷 H

We know, ∆𝑯 = 𝑪𝑷 H 𝑻 − 𝑻𝟎 … … … … … . . (𝟏𝟏)

∆𝑯
𝑻= + 𝑻𝟎 … … … … … … … … … … . (𝟏𝟐)
𝑪𝑷 H

𝑻
 Guess 𝑻, (get the value of 𝝉 = 𝑻  calculate 𝑪𝑷 H from eq. (10)
𝟎
 Use eq. (12) to calculate new 𝑻  match with the guessed value.
 Iterate till the guess value of 𝑻 and calculated value of 𝑻 from eq. (12) match.
Heat Effects
Latent Heat of Pure Substances
Addition or removal of heat to or from a substance  causes change in phase:
S ⇌ L, or L ⇌ V or S ⇌ V
 Latent heat of (phase transition  fusion, vaporization, etc.)
 There is no change in Temperature, and two phases co-exist
 From phase rule, F = 1, only T dependency

𝒅𝑷𝒔𝒂𝒕 ∆𝑯: Latent heat

∆𝑯 = 𝑻 ∆𝑽 𝒅𝑻 …….. (13) ∆𝑽: Volume change during phase transition
Clapeyron equation 𝑷𝒔𝒂𝒕 : Saturation pressure

𝒅𝑷𝒔𝒂𝒕
: slope of the curve of vapour pressure vs. T
𝒅𝑻

Trouton’s rule: latent heat of vaporization of pure liquids at their normal boiling point
∆𝑯𝒏
~𝟏𝟎 …. (14)
𝑹𝑻𝒏

𝑻𝒏 : normal boiling point, K

∆𝑯
∆𝑯𝒏 , 𝑻𝒏 𝒂𝒏𝒅 𝑹: units should be consistence to make the value of 𝑹𝑻𝒏 dimensionless.
𝒏
Heat Effects
Latent Heat of Pure Substances
∆𝑯
For simple fluids, the ratio 𝑹𝑻𝒏 ~ 8 – 13
𝒏

∆𝑯𝒏 𝟏.𝟎𝟗𝟐 𝒍𝒏 𝑷𝒄 −𝟏.𝟎𝟏𝟑 𝑷𝒄 : critical pressure (bar)

Riedel equation: = ……… (15) 𝑻𝒓𝒏 : reduced temperature at 𝑻𝒏
𝑹𝑻𝒏 𝟎.𝟗𝟑𝟎−𝑻𝒓𝒏

For water, equation (15) gives:

∆𝑯𝒏 𝟏. 𝟎𝟗𝟐 𝒍𝒏 𝟐𝟐𝟎. 𝟓𝟓 − 𝟏. 𝟎𝟏𝟑

= = 𝟏𝟑. 𝟓𝟔
𝑹𝑻𝒏 𝟎. 𝟗𝟑𝟎 − 𝟎. 𝟓𝟕𝟕

𝑱 𝑱
∆𝑯𝒏 = 𝟏𝟑. 𝟓𝟔 × 𝟖. 𝟑𝟏𝟒 × 𝟑𝟕𝟑. 𝟏𝟓 = 𝟒𝟐𝟎𝟔𝟓 = 𝟐𝟑𝟑𝟕
𝒎𝒐𝒍 𝒈
𝑱
Value of ∆𝑯𝒏 from steam table: 𝟐𝟐𝟓𝟕 𝒈 error ~ 3.5%.

Estimation of ∆𝑯 of a pure fluid at any temperature, Watson’s equation:

given the value at some other temperature ∆𝑯𝟐 𝟏−𝑻𝒓𝟐 𝟎.𝟑𝟖
= ….. (16)
∆𝑯𝟏 𝟏−𝑻𝒓𝟏
Heat Effects
Standard Heat of Reaction
 Chemical reaction involves either addition or removal of heat
 For the reaction to occur in an isothermal condition, required amount of heat either
to be transferred from the surroundings to the system or system to the surroundings
 Each reaction occur at a particular T

We have seen before that the addition of heat, Q causes the change in enthalpy, H (in
the absence of any shaft work on the system:

∆𝑯 = 𝑸 The enthalpy change, ∆𝐻 is the heat of reaction

If the reactants and products are in their standard states, then the corresponding ∆𝐻 is
the standard heat of reaction

Standard State: A standard state is defined as the state of a substance at specified

pressure, composition, and physical condition as, e.g., gas, liquid, or solid.

Gases: The pure substance in the ideal-gas state at 1 bar

Liquids and solids: The real pure liquid or solid at 1 bar.
Heat Effects
Standard Heat of Reaction
∆𝑯 = 𝑸 The enthalpy change, ∆𝐻 is the heat of reaction

Let us consider the following chemical reaction: 𝒂𝑨 + 𝒃𝑩 → 𝒄𝑪 + 𝒅𝑫

Standard heat of reaction at temperature T:
The enthalpy change when 𝒂 moles of 𝑨 and 𝒃 moles of 𝑩 in their
standard states at temperature T react to form 𝒄 moles of 𝑪 and 𝒅
moles of 𝑫 in their standard states at the same temperature T.

All conditions for a standard state are fixed except temperature, which
is always the temperature of the system.
Standard-state properties are therefore functions of temperature only.

Heat of reaction of reaction depends on the way the stoichiometric

coefficients are written:
1 3 𝑜 𝑜
𝑁2 + 𝐻2 → 𝑁𝐻3 ∆𝐻298 = −46110 𝐽 𝑁2 + 3𝐻2 → 2𝑁𝐻3 ∆𝐻298 = −92220 𝐽
2 2