HEAT EFFECTS (Cha 4) : Outline of Chapter One

1.
HEAT EFFECTS (cha 4)
Outline of Chapter One

Sensible Heat Effect
Latent Heat Effect
Standard State
Standard Heat of Reaction
Standard Heat of Formation
Standard Heat of Combustion
Temperature Dependence of H
Heat Effects of Industrial Application
College of Biological and Chemical Engineering Lecture Notes on Chemical Engineering Thermodynamics II 1
Chemical Eng’g Department Prepared by Dr Sirini & Muhidin Seid
Learning Outcomes
At the end of this chapter students will be able to :

Understand, differentiate and determine sensible and latent heats of pure
substances.
Define and apply standard states.
Calculate and determine heat of reaction, heat of formation, heat of
combustion and their respective standard states.
Apply the knowledge gained on selected chemical industries.
College of Biological and Chemical Engineering Lecture Notes on Chemical Engineering Thermodynamics II
Chemical Eng’g Department
2
Prepared by Dr Sirini & Muhidin Seid
Sensible and Latent Heat Effect
Sensible Heat Effect

 Flow of heat associated with
 Change in T of system – sensible heat flow.
 Without change in T of system – latent heat,
 Sensible heat flow
 Effect on two state functions: U = U(T,V) & H = H(T,P)
Prepared by Dr Sirini & Muhidin Seid3
Sensible Heat …….
 U   U   U 
dU    dT    dV  C V dT    dV
 T  V  V  T  V  T
Second term is zero

Process is constant volume (regardless of substance), or
U is independent of V e.g., ideal gas
In either case
T2
U  C
T1
v dT
For mechanically reversible constant volume process

T2
Q  U   C v dT
T1
Enthalpy: H = H(T,P)
 H   H   H 
dH    dT    dP  C P dT    dP
 T  P  P  T  P  T
Second term is zero if

Process is constant pressure, or
H is independent of V e.g., ideal gas
In either case

T2
H  C
T1
P dT
6
For mechanically reversible constant-pressure process

T2
Q  H   C P dT
T1
CP is not constant; T  40 0C it may be assumed constant

CP is not constant;T > 40 0C it cannot be assumed constant and the
dependence on T is of the form CP = CP(T)
CP or CP c
 α  βT  γT 2  a  bT  2
R R T
The above two forms can be combined into one as given below
CP D
 A  BT  CT  2
2
R T
where either C or D is zero
Ideal Gas State & CPig
Ideal-gas-state:
For gases TD calculations are done in two steps:

1.Evaluation of hypothetical ideal-gas state
2.Correction of ideal-gas state values to real-gas values
9
Ideal-gas state of a real gas (macroscopic view):
Given real gas at T & P, consider thought experiment where
1. P  0 at constant T (gas starts behaving as ideal gas)

2. Bring P back to original value assuming gas continues to behave
ideally
10
Ideal-gas state of a real gas (microscopic view):
Given real gas at T & P, consider behavior of gas where intermolecular i/a
becomes zero
Each real gas have its own characteristic properties in ideal-gas state
e.g.,CPig is different for different gases.

11
Ideal-gas state of a real gas (Properties):
1. EOS is PV = RT
2. U = U(T) & H = H(T)
3. CPig – CVig = R
12
Evaluation of Sensible Heat Integral
Since CP H
T
 T  T0    C P dT  AT 0   1  
B 2 2 C
  D   1
T0   1  T03  3  1    
R T0
R 2 3 T0   
Using T  T0
 1 
T0
 D 
T0   1  T02  2    1 
CP B C
 A   T  T0 
H
 T  T0   2 3 2 
T0 
R
13
Example 1: Temperature Calculations
What is final temperature when heat in the amount of 422 MJ is added to

11.3 kmol of ammonia initially at 533.15 K in a steady-flow process at 1
atm.
Solution:
Q 422  106
Const – P: Q = n(H) H    37.345 kJ/kmol
n 11 .3  10 3
14
Temperature Calculations …….
T2
C igP  D    1 
 R  AT 0   1  T0   1  T0   1  
H  R  dT B 2 2 C 3 3
R 
T1
 2 3 T0   
T0 = 533.15 K,
 - unknown: iterative procedure (home assignment!)
15
Heat Effects Without Temperature Change: Latent Heat
Latent Heat: Heat transfer associated with change of phase

Two-phase system, single species: univariant, (DOF = 1)
dP sat
Clayperon eqn.: H  T V
dT
where H – latent heat, V – volume change accompanying phase change

& Psat – vapor pressure
16
Latent Heat…….
Trouton’s rule: Latent heat of vaporization at normal bp

H n
 10
RT n
Other equation: the equation proposed by Siedel:
17
Standard State
Standard State is a constant reference points (standard states) against which all
comparisons can be made.:
A particular state of a species at T and at specified conditions of P,

composition, and physical condition (e.g., gas, liquid, or solid)
0
Property values at std. state denoted by degree symbol, e.g. C P
18
Standard State……..
19
Standard State……
Standard state
P: 1 atm (earlier days), now 1 bar Composition: states of pure species
Physical state: gases – ideal gas state, liquid & solids – real pure liquid/
solid
For gases: std. state is ideal gas state at 1 bar

20
Standard State……
Standard states for compounds are defined as :

 Solid - pure solid
 Liquid - pure liquid
 Solute - concentration of 1 mol per kg of solvent in a given solvent
 Gas pure gas at 1 atm pressure
 Standard conditions for all reactions of practical interest are defined as 1 atm
pressure and 298 K.
21
Heat of Reaction
Heat of reaction: Heat transfer associated with chemical reaction

Due to difference in the energy associated with reactant and product
molecules.
Consider a rxn carried out at constant T & P with negligible KE & PE, W s
and at steady state conditions
22
Heat of Reaction…..
Then open system energy balance gives, Q = H
Enthalpy change of reaction  heat of reaction,

Heat of rxn also changes with T
Not possible to tabulate heat of rxn for all rxn at useful range of T
 Tabulate data at some reference state & use H calculations to find heat of rxn
at any other temperature.
23
Standard Heat of Reaction
Consider the following reaction carried out at T

aA  bB  lL  mM
Standard Heat of rxn: enthalpy change when a moles of A and b moles of

B react in their std. state at T to form l moles of L and m moles of M in
their standard state at T
24
Standard Heat of Reaction……
Heat of rxn refers to stoichiometric coefficient as written
1 3
N 2  H 2  NH 3 H 0298  46,110 J
2 2
N 2  3H 2  2NH 3 H 0
298  92,220 J
If stoichiometric coefficients are doubled; heat of rxn doubles

Compiling data for std. heat of rxn for all possible rxn is not possible
25
Standard Heat of Reaction…..
Compile Std. ht. of rxn for small set of rxn from which std. heat of rxn for all
other rxn. can be calculated.
Such a set is Standard Heat of Formation
26
Heat of Formation
Heat of rxn is enthalpy change of rxn

Enthalpy is state fn., i.e., change of enthalpy independent of path
Heat of rxn independent of path
Std. ht. of rxn. can be calculated from std. heat of formation rxn.
Heat of rxn depends on temperature.
27
Heat of Formation…
Heat of formation rxn tabulated at 25 0C or 298.15 K

Heat of rxn at any T is calculated using two step procedure
1. Heat of rxn at 298.15 K
2. Change in heat of rxn at desired T from 298.15 K.
28
Standard Heat of Formation
Formation Rxn: a rxn which forms a single compound from its constituent
elements. Stoichiometry such that it results in 1 mol of the compound
Std. ht of formation rxn: H f
0
Std. ht of formation rxn at 298.15 K: H 0f 298

For elements Std. heat of formation is taken as zero
29
Standard Heat of Formation…….
Any rxn can be represented as a combination of a set of formation rxn

e.g., consider the following rxn.
CO 2 (g)  H 2 (g )  CO (g )  H 2 (g)
The pertinent formation rxn are
CO 2 : C(s)  O 2 (g )  CO 2 H 0f 298  393,509 J
30
H2 : element  H 0
f 298 0
1
CO : C(s)  O 2 (g )  CO (g ) H 0f 298  110 ,525 J
2
1
H 2O : H 2 (g)  O 2 (g )  H 2 O(g) H f 298  241,818 J
0
The given rxn. can be written by writing CO2

formation rxn. in reverse mode
31
CO 2  C(s)  O 2 (g ) H 0
f 298  393,509 J
H2 H 0f 298  0
1
C(s)  O 2 (g )  CO (g ) H 0f 298  110 ,525 J
2
1
H 2 (g)  O 2 (g )  H 2 O(g) H 0f 298  241,818 J
2
CO 2 (g)  H 2 (g )  CO (g )  H 2 (g) H  41166 J

0
32
Heat of Combustion
Carrying out formation reaction for all compounds is not easy to carry out
A combustion reaction is defined as a reaction between an element or
compound and oxygen to form specified combustion products.
Can be measured calorimetrically
Data are always based on 1 mol of the substance burned.
Heat of combustion reaction used to determine heat of formation
33
Example 2
Calculate the standard heat at 25 0C for the following reaction:

4HCl (g) + O2 (g) → 2H2O (g) +2Cl2 (g)
Solution:
Standard heats of formation at 298.15 K from Table C.4 are:
HCl (g) : - 92,307 J & H2O (g) : -241,818 J
34
Example 2….
The following combination gives the desired result

4HCl (g) → 2H2 (g) +2Cl2 (g) H°298 = (4)(92,307
2H2 (g) + O2 (g) → 2H2O (g) H°298 = (2)(-241,818)
4HCl (g) + O2 (g) → 2H2O (g) +2Cl2 (g) H°298 = -114,408 J
35
Example 3
A reaction such as the formation of n-butane:
cannot be carried out in practice.

However, this equation results from combination of the following
combustion reactions:
36
Example 3…..
This is the value of the standard heat of formation of n-butane listed in Table
C.4.
37
Variation of Std. Heat of Rxn with Temperature
Heat of rxn is enthalpy change of rxn

H 0   i H 0i
i
where i is the stoichiometric coeff., +ve for products and negative for reactants.
Enthalpy of elements is taken as zero
Þ Heat of formation is equal to the enthalpy of compound
H 0   i H 0fi
i
38
Variation of Std. Heat of Rxn ……
For standard state P is constant (= 1 bar).

Þ Std. state enthalpy are therefore function of T only:
dH  C Pi dT
0
Þ Thus i
  dH    C
i
i i
i
i Pi dT
since i is constant for a reaction above eqn. may be written as
39
 
d 
i i i
 H   d  H 
 i i    C i Pi dT
 i  i
 
dH  d   i H i   
0
 i Pi
 C dT  C 0
P dT
 i  i
dH  C dT 0 0
P
where C 0P   iC Pi
i
40
Integration gives
T
 C o
H o  H o0  R  P
dT
Where To
R
H o & H o0 are std heat of rxn at T and T0 respectively
41
Example 4
Calculate the standard heat of the methanol-synthesis reaction at 800°C:
CO( g )  2 H 2 ( g )  CH 3OH ( g )
Solution: Apply Eqn.:
H 0O   vi H Ofi
i
to the reaction for reference temperature T 0 = 298.15 K and with heat–of-
formation data from Table C.4 :
H 0O  H 298
O
 200,660    110 ,525  90,135 J
42
Example 4…..
Evaluation of H0 at 1073.15 K is done using the following eqn.
T
H 0
H 0
C OP
1073 298
 dT
R T0
R
B 2 2 C 3 3 D    1 
  A  T0   1 
2
T0   1  
2

T0   1  
T0   

 
where T0 is 298.15 K &  = 1073.15/298.15
43
Example 4…..
Evaluation of parameters in above eqn. done using data in Table C.1
i i A 103B 106C 10-5D
CH30H 1 2.211 12.216 -3.45 0.000
CO -1 3.376 0.557 0.000 -0.031

H2 -2 3.249 0.422 0.000 0.083
44
Example 4…..
From its definition,

A  (1)( 2.211)  (1)(3.376)  (2)(3.249)  7.663
Similarly,
3
B  10.815 10 C  3.450  10 6
D  0.135  10 5
Then by Eqn.:
45
Example 4…..
T
C OP
H 0
1073 H 0
298 R dT 
T0
R
 10.815  10 3 2 2  3.450  10 6 3 3   1,615.5R
  7.663 T0   1 
2
T0   1   2
 T0   1   
 R
  0.135  10    1 
5

    
 T0    
H1073
0
 90,135  8.314(1,615.5)  103,566 J
46
Heat Effect of Industrial Reactions
Industrial rxns :
 are rarely carried on at standard states.
 may not go to completion
 Tf may be different from Ti
 Inert species and several side rxns may present.
However, calculations of the heat effect will be the same.
 It will be clear with the following examples
47
Heat Effect of Industrial Reactions
Example 5.
What is the maximum temperature that can be reached by the combustion
of methane with 20% excess air? Both the methane and the air enter the
burner at 25°C.
Solution:
The reaction is CH 4  2O2 ( g )  CO2  2 H 2O( g )
for which, H 298
0
 393,509  (2)( 214,818)  (74,520)  802,625 J
48
Example 5. ……
Maximum attainable temperature (called the theoretical flame Temperature)

is sought:
Maximum T occurs when all heat released is assimilated by the system
Assume:
1.The combustion reaction goes to completion adiabatically (Q=0).

2. The kinetic and potential energy changes are negligible.
49
Example 5. ……
3. The Ws=0.
The overall energy balance for the process reduces to
H=0
For calculation of the final temperature, any convenient path between the
initial and final states may be used.
50
Example 5. ……
51
Example 5. ……
Basis: one mole of methane burned

Quantities of oxygen and nitrogen supplied by the entering air:
Moles O2 required = 2.0

Moles excess O2 = (0.2)(2.0) = 0.4
Moles N2 required = (2.4)(79/21) = 9.03
52
Example 5 ……
The gases leaving the burner contains 1 mol CO2, 2 mol H2O(g), 0.4 mol O2, and 9.03
mol N2.
Since the enthalpy change must be independent of path,

H 0
298  H  H  0
0
p
The enthalpy change of the products as they are heated from 298.15 K to T is
53
Example 5 ……
H 0P  C OP (T  298.15)
H
where we define C OP as the mean heat capacity for the total product stream
H
C O
P H  n i C O
P H
i
Since C=0 for each product gas (Table C.1), Eq. yields:
54
Example 5 ……
55
Example 5 ……
Data from Table C.1 are combined as follows:

A   n i A i  (1)(5.457)  (2)(3.470)  (0.4)(3.639)  (9.03)(3.280)
i
 43.471
Similarly,
B   n i Bi  9.502 10 3
i
and
D   n i Di  0.645  105
i
56
Example 5 ……
For the product stream (C PO ) H / R is therefore represented by :
MCPH(298.15, T;43.471,9 .502E - 3,0.0,-0.645E  5)
To solve the required T

H O298
T  298.15 - O
CP
H
57
Example 5 ……
C OP
Because the mean heat capacities H depend on T,
first evaluate for an assumed value of T > 298.15,
C OP
H
substitute the result in the preceding equation .

This yields a new value of T for which C is reevaluated. O
P H
The procedure continues to convergence on the final value,

T=2,066K or 1,793°C
58
Example 6
59
Example 6 ……
Solution
60
Example 6 ……
61
Example 6 ……
62
Example 6 ……
63
Example 6 ……
64
Example 6 ……
65

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1.

HEAT EFFECTS (cha 4)

Outline of Chapter One

At the end of this chapter students will be able to :

Sensible Heat Effect

Second term is zero

For mechanically reversible constant volume process

Second term is zero if

In either case

For mechanically reversible constant-pressure process

CP is not constant; T  40 0C it may be assumed constant

Ideal Gas State & CPig

For gases TD calculations are done in two steps:

Ideal-gas state of a real gas (macroscopic view):

Given real gas at T & P, consider thought experiment where

1. P  0 at constant T (gas starts behaving as ideal gas)

Ideal-gas state of a real gas (microscopic view):

e.g.,CPig is different for different gases.

Ideal-gas state of a real gas (Properties):

2. U = U(T) & H = H(T)

Evaluation of Sensible Heat Integral

What is final temperature when heat in the amount of 422 MJ is added to

Latent Heat: Heat transfer associated with change of phase

where H – latent heat, V – volume change accompanying phase change

Trouton’s rule: Latent heat of vaporization at normal bp

Other equation: the equation proposed by Siedel:

A particular state of a species at T and at specified conditions of P,

P: 1 atm (earlier days), now 1 bar Composition: states of pure species

For gases: std. state is ideal gas state at 1 bar

Standard states for compounds are defined as :

Heat of reaction: Heat transfer associated with chemical reaction

Then open system energy balance gives, Q = H

Enthalpy change of reaction  heat of reaction,

Consider the following reaction carried out at T

Standard Heat of rxn: enthalpy change when a moles of A and b moles of

Heat of rxn refers to stoichiometric coefficient as written

If stoichiometric coefficients are doubled; heat of rxn doubles

Such a set is Standard Heat of Formation

Heat of rxn is enthalpy change of rxn

Heat of formation rxn tabulated at 25 0C or 298.15 K

Std. ht of formation rxn at 298.15 K: H 0f 298

Any rxn can be represented as a combination of a set of formation rxn

CO 2 : C(s)  O 2 (g )  CO 2 H 0f 298  393,509 J

The given rxn. can be written by writing CO2

CO 2 (g)  H 2 (g )  CO (g )  H 2 (g) H  41166 J

Calculate the standard heat at 25 0C for the following reaction:

The following combination gives the desired result

A reaction such as the formation of n-butane:

cannot be carried out in practice.

Heat of rxn is enthalpy change of rxn

For standard state P is constant (= 1 bar).

since i is constant for a reaction above eqn. may be written as

H o & H o0 are std heat of rxn at T and T0 respectively

Calculate the standard heat of the methanol-synthesis reaction at 800°C:

Evaluation of H0 at 1073.15 K is done using the following eqn.

Evaluation of parameters in above eqn. done using data in Table C.1

i i A 103B 106C 10-5D

CH30H 1 2.211 12.216 -3.45 0.000

CO -1 3.376 0.557 0.000 -0.031

From its definition,

Maximum attainable temperature (called the theoretical flame Temperature)

1.The combustion reaction goes to completion adiabatically (Q=0).