Heat of Reaction for the Case

of Incomplete Reactions
 In the case where some species react and others do not,
only those species which react are considered during
computation of the heat of reaction at reference
conditions (25℃ and 1 atm.).

24/05/2013 CP 105 CHAPTER 4 1

  Example 4.12
An iron pyrite ore containing 85% FeS2 and 15%
gangue (inert, dirt, rock, etc.) is roasted with 200%
excess air according to the reaction:
𝟒𝐅𝐞𝐒𝟐 + 𝟏𝟏𝐎𝟐 → 𝟐𝐅𝐞𝟐 𝐎𝟑 + 𝟖𝐒𝐎𝟐
in order to produce SO2. All the gangue and the Fe2O3
end up on the solid waste product (cinder) which
analyses 4.0% FeS2. Determine the standard heat of
reaction per kilogram of ore. (Molecular weights:
𝐅𝐞𝐒𝟐 = 120, 𝐅𝐞𝟐 𝐎𝟑 = 160, 𝐒𝐎𝟐 = 64).
Solution:
24/05/2013 CP 105 CHAPTER 4 2
 Product, P = ?
SO2:
O2:
N2:
Ore, F = 100 kg Cinder, C = ?
Roaster
FeS2 : 85% Fe2O3 :
Gangue (I): 15% FeS2 :4.0%
200% excess air, Air = ? Gangue (I):
O2: 21%
N2: 79%
𝟒𝐅𝐞𝐒𝟐 + 𝟏𝟏𝐎𝟐 → 𝟐𝐅𝐞𝟐 𝐎𝟑 + 𝟖𝐒𝐎𝟐
Basis: 100 kg of pyrite ore.
24/05/2013 CP 105 CHAPTER 4 3
 FeS2 fed into a roaster:

𝟎. 𝟖𝟓 𝟏𝟎𝟎 𝐤𝐠. 𝐅𝐞𝐒𝟐 𝟏 𝐤𝐠𝐦𝐨𝐥. 𝐅𝐞𝐒𝟐

∴ 𝐗 𝐅𝐅𝐞𝐒𝟐 . 𝐅 =
𝟏𝟐𝟎 𝐤𝐠. 𝐅𝐞𝐒𝟐

= 𝟎. 𝟕𝟎𝟖𝟑 𝐤𝐠𝐦𝐨𝐥. 𝐅𝐞𝐒𝟐

Gangue (I) fed into a roaster:

= 𝟎. 𝟏𝟓 𝟏𝟎𝟎 = 𝟏𝟓 𝐤𝐠. 𝐈
Gangue (I) is a tie component:
∴ Gangue (I) in the cinder stream = 𝟏𝟓 𝐤𝐠. 𝐈
24/05/2013 CP 105 CHAPTER 4 4
 𝟎. 𝟕𝟎𝟖𝟑 𝐤𝐦𝐨𝐥. 𝐅𝐞𝐒𝟐 𝟏𝟏 𝐤𝐦𝐨𝐥. 𝐎𝟐
𝐓𝐡𝐞𝐨𝐫𝐞𝐭𝐢𝐜𝐚𝐥 𝐎𝟐 =
𝟒 𝐤𝐦𝐨𝐥. 𝐅𝐞𝐒𝟐
= 𝟏. 𝟗𝟒𝟕𝟖 𝐤𝐠𝐦𝐨𝐥. 𝐎𝟐
𝟐𝟎𝟎
𝐎𝟐 𝐬𝐮𝐩𝐩𝐥𝐢𝐞𝐝 = + 𝟏 𝟏. 𝟗𝟒𝟕𝟖 = 𝟓. 𝟖𝟒𝟑𝟒 𝐤𝐠𝐦𝐨𝐥. 𝐎𝟐
𝟏𝟎𝟎
𝟓. 𝟖𝟒𝟑𝟒 𝐤𝐠𝐦𝐨𝐥. 𝐎𝟐 𝟕𝟗 𝐤𝐠𝐦𝐨𝐥. 𝐍𝟐
𝐍𝟐 𝐬𝐮𝐩𝐩𝐥𝐢𝐞𝐝 =
𝟐𝟏 𝐤𝐠𝐦𝐨𝐥. 𝐎𝟐
= 𝟐𝟏. 𝟗𝟖𝟐𝟑 𝐤𝐠𝐦𝐨𝐥. 𝐍𝟐
N2 is a tie component;
∴ N2 in the product stream = 𝟐𝟏. 𝟗𝟖𝟐𝟑 𝐤𝐠𝐦𝐨𝐥. 𝐍𝟐
24/05/2013 CP 105 CHAPTER 4 5
 Let amount of Fe2O3 produced and FeS2 unreacted be a
and b kgmoles, respectively:

𝐗 𝐂𝐅𝐞𝟐 𝐎𝟑 . 𝐂 = 𝐚 𝐤𝐠𝐦𝐨𝐥𝐞𝐬, 𝐗 𝐂𝐅𝐞𝐒𝟐 . 𝐂 = 𝐛 𝐤𝐠𝐦𝐨𝐥𝐞𝐬

Therefore, the cinder stream C in kg;

𝐂 = 𝐦𝐂𝐅𝐞𝟐 𝐎𝟑 + 𝐦𝐂𝐅𝐞𝐒𝟐 + 𝐦𝐂𝐈

= 𝟏𝟔𝟎 𝐗 𝐂𝐅𝐞𝟐 𝐎𝟑 . 𝐂 + 𝟏𝟐𝟎 𝐗 𝐂𝐅𝐞𝐒𝟐 . 𝐂 +𝟏𝟓

= 𝟏𝟔𝟎𝐚 + 𝟏𝟐𝟎𝐛 + 𝟏𝟓
∴ 𝐂 = 𝟏𝟔𝟎𝐚 + 𝟏𝟐𝟎𝐛 + 𝟏𝟓 𝐤𝐠
24/05/2013 CP 105 CHAPTER 4 6
 Mass fraction of FeS2 in the cinder stream:
𝐦𝐂𝐅𝐞𝐒𝟐 𝟏𝟐𝟎 𝐗 𝐂𝐅𝐞𝐒𝟐 . 𝐂 𝟏𝟐𝟎𝐛
𝟎. 𝟎𝟒 = = =
𝐂 𝐂 𝟏𝟔𝟎𝐚 + 𝟏𝟐𝟎𝐛 + 𝟏𝟓
−𝟔. 𝟒𝐚 + 𝟏𝟏𝟓. 𝟐𝐛 = 𝟎. 𝟔 (1)
Let us now perform elemental balances:
𝐅𝐞: 𝐗 𝐅𝐅𝐞𝐒𝟐 . 𝐅 = 𝟐𝐗 𝐂𝐅𝐞𝟐 𝐎𝟑 . 𝐂 + 𝐗 𝐂𝐅𝐞𝐒𝟐 . 𝐂
𝟎. 𝟕𝟎𝟖𝟑 = 𝟐𝐚 + 𝐛
𝟐𝐚 + 𝐛 = 𝟎. 𝟕𝟎𝟖𝟑 (2)
Solving equation 1 and 2 simultaneously, gives:
∴ 𝐚 = 𝟎. 𝟑𝟒𝟐𝟎 𝐤𝐠𝐦𝐨𝐥𝐞𝐬, 𝐛 = 𝟎. 𝟎𝟐𝟒𝟑 𝐤𝐠𝐦𝐨𝐥𝐞𝐬
24/05/2013 CP 105 CHAPTER 4 7
 𝐒: 𝟐𝐗 𝐅𝐅𝐞𝐒𝟐 . 𝐅 = 𝐗 𝐏𝐒𝐎𝟐 . 𝐏 + 𝟐𝐗 𝐂𝐅𝐞𝐒𝟐 . 𝐂

𝟐 𝟎. 𝟕𝟎𝟖𝟑 = 𝐗 𝐏𝐒𝐎𝟐 . 𝐏 + 𝟐 𝟎. 𝟎𝟐𝟒𝟑

∴ 𝐗 𝐏𝐒𝐎𝟐 . 𝐏 = 𝟏. 𝟑𝟔𝟖𝟎 𝐤𝐠𝐦𝐨𝐥𝐞𝐬

𝐀 𝐏 𝐏 𝐂
𝐎: 𝟐𝐗 𝐎 𝟐
. 𝐀 = 𝟐𝐗 𝐒𝐎𝟐 . 𝐏 + 𝟐𝐗 𝐎𝟐 . 𝐏 + 𝟑𝐗 𝐅𝐞𝟐 𝐎𝟑 . 𝐂

𝟐 𝟓. 𝟖𝟒𝟑𝟒 = 𝟐 𝟏. 𝟑𝟔𝟖𝟎 + 𝟐𝐗 𝐏𝐎𝟐 . 𝐏 + 𝟑 𝟎. 𝟑𝟒𝟐𝟎

∴ 𝐗 𝐏𝐎𝟐 . 𝐏 = 𝟑. 𝟗𝟔𝟐𝟒 𝐤𝐠𝐦𝐨𝐥𝐞𝐬

Thus, this is how the block diagram presentation of this
problem now looks like:
24/05/2013 CP 105 CHAPTER 4 8
 Product, P = ?
SO2 = 1.3680 kmol.
O2 = 3.9624 kmol.
N2 = 21.9823 kmol.
Ore, F = 100 kg Cinder, C = ?
Roaster
FeS2 = 0.7083 kmol. Fe2O3 = 0.3420 kmol.
Gangue (I) = 15 kg FeS2 = 0.0243 kmol.
Gangue (I) = 15 kg
200% excess air, Air = ?
O2: 21% = 5.8434 kmol.
N2: 79% = 21.9823 kmol.
24/05/2013 CP 105 CHAPTER 4 9
 𝟒𝐅𝐞𝐒𝟐 + 𝟏𝟏𝐎𝟐 → 𝟐𝐅𝐞𝟐 𝐎𝟑 + 𝟖𝐒𝐎𝟐

𝟎. 𝟑𝟒𝟐𝟎 𝐤𝐠𝐦𝐨𝐥. 𝐅𝐞𝟐 𝐎𝟑 𝟒 𝐤𝐠𝐦𝐨𝐥. 𝐅𝐞𝐒𝟐

𝐧𝐅𝐞𝐒𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 =
𝟐 𝐤𝐠𝐦𝐨𝐥. 𝐅𝐞𝟐 𝐎𝟑
∴ 𝐧𝐅𝐞𝐒𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = 𝟎. 𝟔𝟖𝟒𝟎 𝐤𝐠𝐦𝐨𝐥.

𝟎. 𝟑𝟒𝟐𝟎 𝐤𝐠𝐦𝐨𝐥. 𝐅𝐞𝟐 𝐎𝟑 𝟏𝟏 𝐤𝐠𝐦𝐨𝐥. 𝐎𝟐

𝐧𝐎𝟐 𝐜𝐨𝐧𝐬𝐮𝐦𝐞𝐝 =
𝟐 𝐤𝐠𝐦𝐨𝐥. 𝐅𝐞𝟐 𝐎𝟑
∴ 𝐧𝐎𝟐 𝐜𝐨𝐧𝐬𝐮𝐦𝐞𝐝 = 𝟏. 𝟖𝟖𝟏𝟎 𝐤𝐠𝐦𝐨𝐥.

The standard heat of reaction can now be calculated:

24/05/2013 CP 105 CHAPTER 4 10
 ^𝐨 ^𝐨
By definition: ∆𝐇𝐟,𝐎𝟐 = 𝟎, ∆𝐇𝐟,𝐍𝟐 = 𝟎

The gangue does not react.

The heats of formation from tabulated data:

^𝐨 ^
𝐨 𝐨
∆𝐇𝐫𝐱𝐧,𝐓 = 𝐧𝐢 𝐇𝐟,𝐢 − 𝐧𝐢 𝐇𝐟,𝐢
𝐫𝐞𝐟
𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐬 𝐑𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬
24/05/2013 CP 105 CHAPTER 4 11
 ^𝐨 ^𝐨 ^𝐨 ^𝐨
𝐨 𝐧𝐅𝐞𝟐𝐎𝟑 𝐇𝐟,𝐅𝐞𝟐𝐎𝟑 + 𝐧𝐒𝐎𝟐 𝐇𝐟,𝐒𝐎𝟐 − 𝐧𝐅𝐞𝐒𝟐 𝐇𝐟,𝐅𝐞𝐒𝟐 + 𝐧𝐎𝟐 𝐇𝐟,𝐎𝟐
∆𝐇𝐫𝐱𝐧 =

= 342 −𝟖𝟐𝟐. 𝟏𝟓𝟔 + 𝟏𝟑𝟔𝟖 −𝟐𝟗𝟔. 𝟗𝟎 −

𝟔𝟖𝟒 −𝟏𝟕𝟕. 𝟗 + 𝟏𝟖𝟖𝟏 𝟎

𝐨 𝐤𝐉
∆𝐇𝐫𝐱𝐧,𝐓 =−𝟓. 𝟔𝟓𝟔𝟓 × 𝟏𝟎𝟓
𝐫𝐞𝐟
𝟏𝟎𝟎 𝐤𝐠. 𝐎𝐫𝐞

𝐨 𝐤𝐉
∴ ∆𝐇𝐫𝐱𝐧,𝐓 = −𝟓𝟔𝟓𝟔. 𝟓
𝐫𝐞𝐟 𝐤𝐠. 𝐎𝐫𝐞

24/05/2013 CP 105 CHAPTER 4 12

 Alternatively, the standard heat of reaction can be
calculated using the stoichiometric coefficients in the
chemical equation with the amount of FeS2 reacted:
𝟒𝐅𝐞𝐒𝟐 + 𝟏𝟏𝐎𝟐 → 𝟐𝐅𝐞𝟐 𝐎𝟑 + 𝟖𝐒𝐎𝟐
^𝐨 ^𝐨 ^𝐨 ^𝐨
𝐨 𝐧𝐅𝐞𝟐𝐎𝟑 𝐇𝐟,𝐅𝐞𝟐𝐎𝟑 + 𝐧𝐒𝐎𝟐 𝐇𝐟,𝐒𝐎𝟐 − 𝐧𝐅𝐞𝐒𝟐 𝐇𝐟,𝐅𝐞𝐒𝟐 + 𝐧𝐎𝟐 𝐇𝐟,𝐎𝟐
∆𝐇𝐫𝐱𝐧 =

𝐨 =
∆𝐇𝐫𝐱𝐧 2 −𝟖𝟐𝟐. 𝟏𝟓𝟔 + 𝟖 −𝟐𝟗𝟔. 𝟗𝟎 − 𝟒 −𝟏𝟕𝟕. 𝟗 + 𝟏𝟏 𝟎
𝐨
𝐤𝐉
∆𝐇𝐫𝐱𝐧 =−𝟑𝟑𝟎𝟕. 𝟗𝟏𝟐
𝟒 𝐠𝐦𝐨𝐥. 𝐅𝐞𝐒𝟐
𝐨 −𝟑𝟑𝟎𝟕. 𝟗𝟏𝟐 𝐤𝐉 𝟔𝟖𝟒 𝐠𝐦𝐨𝐥. 𝐅𝐞𝐒𝟐 𝐤𝐉
∆𝐇𝐫𝐱𝐧 = = −𝟓𝟔𝟓𝟔. 𝟓
𝟒 𝐠𝐦𝐨𝐥. 𝐅𝐞𝐒𝟐 𝟏𝟎𝟎 𝐤𝐠. 𝐎𝐫𝐞 𝐤𝐠. 𝐎𝐫𝐞
24/05/2013 CP 105 CHAPTER 4 13
 Energy Balances when the
Products and Reactants are
not at 25C
 The reference temperature for the standard heats of
formation is 250C

 However, in practice, the products and reactants may

enter or leave the system at temperatures that are not
equal to this reference temperature.

24/05/2013 CP 105 CHAPTER 4 14

 Consider the following case:

𝐀: 𝐧𝐀 , 𝐓𝐀 Reactor 𝐂: 𝐧𝐂 , 𝐓𝐂

Reaction at
(Reactants) (Products)
T
𝐁: 𝐧𝐁 , 𝐓𝐁 𝐃: 𝐧𝐃 , 𝐓𝐃
𝐐 = ∆𝐇𝐫𝐱𝐧

The reaction: 𝐚𝐀 + 𝐛𝐁 → 𝐜𝐂 + 𝐝𝐃
Steps that needed to be followed for calculating ∆𝐇𝐫𝐱𝐧,𝐓
for this situation are as follows:
24/05/2013 CP 105 CHAPTER 4 15
 1) Choose a reference state (normally Tref = 25C with Pref
= 1 atm) whereby the heats of formation of the various
species involved in the reaction are known.
2) Calculate the sensible heat for each process stream
using the respective heat capacities: ^ 𝐓
∆𝐇 = 𝐂𝐏 𝐝𝐓
𝐓𝐫𝐞𝐟
3) Retrieve/obtain enthalpy values of the various
compounds from Tables or data base.
𝐨
4) Calculate ∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
.
5) Calculate ∆𝐇𝐫𝐱𝐧, 𝐓 using:
𝐨 + ∆𝐇 − ∆𝐇
∆𝐇𝐫𝐱𝐧, 𝐓 = ∆𝐇𝐫𝐱𝐧 𝐏 𝐑
24/05/2013 CP 105 CHAPTER 4 16
  Example 4.13
The gas phase reaction:
𝐂𝐎𝟐 (𝐠) + 𝟒𝐇𝟐 (𝐠) → 𝟐𝐇𝟐 𝐎(𝐠) + 𝐂𝐇𝟒 (𝐠)
proceeds with 100% conversion. Estimate the heat that
must be provided or removed if the gases enter and leave
the reaction vessel at 500oC (773 K).
𝐂𝐎 = 𝟏 𝐠𝐦𝐨𝐥. Reactor 𝐇 𝐎 = 𝟐 𝐠𝐦𝐨𝐥.
𝟐 (𝐠) 𝟐 (𝐠)
Reaction
𝐓𝐢𝐧 = 𝟓𝟎𝟎℃ 𝐓𝐨 = 𝟓𝟎𝟎℃
100% conversion.
𝐇𝟐 (𝐠)= 𝟒 𝐠𝐦𝐨𝐥. 𝐂𝐇𝟒 (𝐠) = 𝟏 𝐠𝐦𝐨𝐥.
𝐐
Basis: 1gmole of 𝐂𝐎𝟐 (𝐠) .
24/05/2013 CP 105 CHAPTER 4 17
  Recall the energy balance equation for open system:
^ ^ ^
∆𝐄 = −∆ 𝐦 𝐇 + 𝐊 + 𝐏 + 𝐐 − 𝐖
Simplifications of the energy balance equation;
a steady state process: ΔE = 0
no potential and kinetic energies: ΔP = 0, ΔK = 0,
no mechanical movements of the system: W = 0.
Thus, the energy balance equation can be reduced to:
^
𝐐 = 𝐦. ∆𝐇 = ∆𝐇 = ∆𝐇𝐫𝐱𝐧,𝐓
𝐨
∆𝐇𝐫𝐱𝐧, 𝐓 = ∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
+ ∆𝐇𝐏 − ∆𝐇𝐑
24/05/2013 CP 105 CHAPTER 4 18
 ^𝐨 ^
𝐨 𝐨
∆𝐇𝐫𝐱𝐧,𝐓 = 𝐧𝐢 𝐇𝐟,𝐢 − 𝐧𝐢 𝐇𝐟,𝐢
𝐫𝐞𝐟
𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐬 𝐑𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬
^𝐨 ^𝐨 ^𝐨 ^𝐨
= 𝐧𝐇𝟐 𝐎 ∆𝐇𝐟,𝐇𝟐 𝐎 + 𝐧𝐂𝐇𝟒 ∆𝐇𝐟,𝐂𝐇𝟒 − 𝐧𝐂𝐎𝟐 ∆𝐇𝐟,𝐂𝐎𝟐 + 𝐧𝐇𝟐 ∆𝐇𝐟,𝐇𝟐

The standard heats of formation data (at 25oC) from the

literature:

Reference temperature: 𝐓𝐫𝐞𝐟 = 𝟐𝟓℃ = 𝟐𝟗𝟖 𝐊

24/05/2013 CP 105 CHAPTER 4 19
 𝐨 ^𝐨 ^𝐨 ^𝐨 ^𝐨
∆𝐇𝐫𝐱𝐧 = 𝐧𝐇𝟐 𝐎 ∆𝐇𝐟,𝐇𝟐 𝐎 + 𝐧𝐂𝐇𝟒 ∆𝐇𝐟,𝐂𝐇𝟒 − 𝐧𝐂𝐎𝟐 ∆𝐇𝐟,𝐂𝐎 𝟐
+ 𝐧𝐇𝟐 ∆𝐇𝐟,𝐇𝟐

= 𝟐 −𝟐𝟒𝟏. 𝟖𝟑 + 𝟏 −𝟕𝟒. 𝟖𝟓 − 𝟏 −𝟑𝟗𝟑. 𝟓𝟏 + 𝟒 𝟎

𝐨
∴ ∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
= −𝟏𝟔𝟓 𝐤𝐉
𝐓𝐨
∆𝐇𝐏 = 𝐧𝐢 𝐂𝐏𝐢 𝐝𝐓
𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐬 𝐓𝐫𝐞𝐟
J
The Cp equations in with T in K from the
gmol.K
literature:
𝐂𝐏𝐂𝐎 = 𝟐𝟔. 𝟕𝟓 + 𝟒𝟐. 𝟐𝟔 × 𝟏𝟎−𝟑 𝐓 − 𝟏𝟒. 𝟐𝟓 × 𝟏𝟎−𝟔 𝐓 𝟐
𝟐
24/05/2013 CP 105 CHAPTER 4 20
 𝐂𝐏𝐇 = 𝟐𝟔. 𝟖𝟖 + 𝟒. 𝟑𝟓 × 𝟏𝟎−𝟑 𝐓 − 𝟎. 𝟑𝟑 × 𝟏𝟎−𝟔 𝐓 𝟐
𝟐

𝐂𝐏𝐇 = 𝟐𝟗. 𝟏𝟔 + 𝟏𝟒. 𝟒𝟗 × 𝟏𝟎−𝟑 𝐓 − 𝟐. 𝟎𝟐 × 𝟏𝟎−𝟔 𝐓 𝟐

𝟐𝐎

𝐂𝐏𝐂𝐇 = 𝟏𝟑. 𝟒𝟏 + 𝟕𝟕. 𝟎𝟑 × 𝟏𝟎−𝟑 𝐓 − 𝟏𝟖. 𝟕𝟒 × 𝟏𝟎−𝟔 𝐓 𝟐

𝟒

24/05/2013 CP 105 CHAPTER 4 21

 𝐓𝐨
∆𝐇𝐏 = 𝐧𝐢 𝐂𝐏𝐢 𝐝𝐓
𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐬 𝐓𝐫𝐞𝐟

𝐓𝐨,𝐇𝟐 𝐎 𝐓𝐨,𝐂𝐇𝟒
= 𝐧𝐇𝟐 𝐎 𝐂𝐏𝐇 𝐎 𝐝𝐓 + 𝐧𝐂𝐇𝟒 𝐂𝐏𝐂𝐇 𝐝𝐓
𝟐 𝟒
𝐓𝐫𝐞𝐟 𝐓𝐫𝐞𝐟

𝟕𝟕𝟑 𝟕𝟕𝟑
= 𝐧𝐇𝟐 𝐎 𝐂𝐏𝐇 𝐎 𝐝𝐓 + 𝐧𝐂𝐇𝟒 𝐂𝐏𝐂𝐇 𝐝𝐓
𝟐 𝟒
𝟐𝟗𝟖 𝟐𝟗𝟖

𝟕𝟕𝟑
= 𝐧𝐇𝟐 𝐎 𝐂𝐏𝐇 + 𝐧𝐂𝐇𝟒 𝐂𝐏𝐂𝐇 𝐝𝐓
𝟐𝐎 𝟒
𝟐𝟗𝟖
24/05/2013 CP 105 CHAPTER 4 22
 𝐧𝐇𝟐 𝐎 𝐂𝐏𝐇 + 𝐧𝐂𝐇𝟒 𝐂𝐏𝐂𝐇 :
𝟐𝐎 𝟒

𝐧𝐇𝟐 𝐎 𝐂𝐏𝐇 + 𝐧𝐂𝐇𝟒 𝐂𝐏𝐂𝐇 =

𝟐𝐎 𝟒

𝟕𝟏. 𝟕𝟑 + 𝟏𝟎𝟔. 𝟎𝟏 × 𝟏𝟎−𝟑 𝐓 − 𝟐𝟐. 𝟕𝟖 × 𝟏𝟎−𝟔 𝐓 𝟐

Therefore;
𝟕𝟕𝟑
𝟕𝟏. 𝟕𝟑 + 𝟏𝟎𝟔. 𝟎𝟏 × 𝟏𝟎−𝟑 𝐓 − 𝟐𝟐. 𝟕𝟖 × 𝟏𝟎−𝟔 𝐓 𝟐 𝐝𝐓
𝟐𝟗𝟖
24/05/2013 CP 105 CHAPTER 4 23
 ∴ ∆𝐇𝐏 = 𝟓𝟕. 𝟕𝟑 𝐤𝐉
𝐓𝐢𝐧
∆𝐇𝐑 = 𝐧𝐢 𝐂𝐏𝐢 𝐝𝐓
𝐑𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬 𝐓𝐫𝐞𝐟
𝐓𝐢𝐧, 𝐂𝐎𝟐 𝐓𝐢𝐧, 𝐇𝟐
= 𝐧𝐂𝐎𝟐 𝐂𝐏𝐂𝐎 𝐝𝐓 + 𝐧𝐇𝟐 𝐂𝐏𝐇 𝐝𝐓
𝟐 𝟐
𝐓𝐫𝐞𝐟 𝐓𝐫𝐞𝐟

𝟕𝟕𝟑 𝟕𝟕𝟑
= 𝐧𝐂𝐎𝟐 𝐂𝐏𝐂𝐎 𝐝𝐓 + 𝐧𝐇𝟐 𝐂𝐏𝐇 𝐝𝐓
𝟐 𝟐
𝟐𝟗𝟖 𝟐𝟗𝟖
𝟕𝟕𝟑
= 𝐧𝐂𝐎𝟐 𝐂𝐏𝐂𝐎 + 𝐧𝐇𝟐 𝐂𝐏𝐇 𝐝𝐓
𝟐 𝟐
𝟐𝟗𝟖
24/05/2013 CP 105 CHAPTER 4 24
 𝐧𝐂𝐎𝟐 𝐂𝐏𝐂𝐎 + 𝐧𝐇𝟐 𝐂𝐏𝐇 :
𝟐 𝟐

𝐧𝐂𝐎𝟐 𝐂𝐏𝐂𝐎 + 𝐧𝐇𝟐 𝐂𝐏𝐇 =

𝟐 𝟐

𝟏𝟑𝟒. 𝟐𝟕 + 𝟓𝟗. 𝟔𝟔 × 𝟏𝟎−𝟑 𝐓 − 𝟏𝟓. 𝟓𝟕 × 𝟏𝟎−𝟔 𝐓 𝟐

Therefore;
𝟕𝟕𝟑
𝟏𝟑𝟒. 𝟐𝟕 + 𝟓𝟗. 𝟔𝟔 × 𝟏𝟎−𝟑 𝐓 − 𝟏𝟓. 𝟓𝟕 × 𝟏𝟎−𝟔 𝐓 𝟐 𝐝𝐓
𝟐𝟗𝟖
24/05/2013 CP 105 CHAPTER 4 25
 ∴ ∆𝐇𝐑 = 𝟕𝟔. 𝟔𝟗 𝐤𝐉
𝐨
∆𝐇𝐫𝐱𝐧, 𝐓 = ∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
+ ∆𝐇𝐏 − ∆𝐇𝐑

= −𝟏𝟔𝟓 + 𝟓𝟕. 𝟕𝟑 − 𝟕𝟔. 𝟔𝟗

𝐤𝐉
∴ ∆𝐇𝐫𝐱𝐧, 𝐓 = −𝟏𝟖𝟑. 𝟗𝟔
𝐦𝐨𝐥. 𝐂𝐎𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝
Therefore;
𝐤𝐉
𝐐 = ∆𝐇𝐫𝐱𝐧, 𝐓 = −𝟏𝟖𝟑. 𝟗𝟔
𝐦𝐨𝐥. 𝐂𝐎𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝
𝐤𝐉
∴ 𝐐 = −𝟏𝟖𝟑. 𝟗𝟔
𝐦𝐨𝐥. 𝐂𝐎𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝
24/05/2013 CP 105 CHAPTER 4 26
 Alternatively:
The sensible heats ∆𝐇𝐏 and ∆𝐇𝐑 can also be found using
data tabulated on Table 4.4 (Page 391) and Table D.2 (Page
674) of David Himmelblau’s book.
From the previous calculation;
𝐨
∴ ∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
= −𝟏𝟔𝟓 𝐤𝐉 with 𝐓𝐫𝐞𝐟 = 𝟐𝟓℃ = 𝟐𝟗𝟖 𝐊

^ ^
∆𝐇𝐏 = 𝐧𝐢 𝐇𝐢,𝐓𝐨 − 𝐇𝐢,𝐓𝐫𝐞𝐟
𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐬
^ ^ ^ ^
= 𝐧𝐂𝐇𝟒 𝐇𝐂𝐇𝟒 ,𝟕𝟕𝟑 𝐊 − 𝐇𝐂𝐇𝟒 ,𝟐𝟗𝟖 𝐊 +𝐧𝐇𝟐 𝐎 𝐇𝐇𝟐 𝐎,𝟕𝟕𝟑 𝐊 − 𝐇𝐇𝟐 𝐎,𝟐𝟗𝟖 𝐊

24/05/2013 CP 105 CHAPTER 4 27

 ^ ^
∆𝐇𝐑 = 𝐧𝐢 𝐇𝐢,𝐓𝐢𝐧 − 𝐇𝐢,𝐓𝐫𝐞𝐟
𝐑𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬
^ ^ ^ ^
= 𝐧𝐂𝐎𝟐 𝐇𝐂𝐎𝟐 ,𝟕𝟕𝟑 𝐊 − 𝐇𝐂𝐎𝟐 ,𝟐𝟗𝟖 𝐊 + 𝐧𝐇𝟐 𝐇𝐇𝟐 ,𝟕𝟕𝟑 𝐊 − 𝐇𝐇𝟐 ,𝟐𝟗𝟖 𝐊

From Table 4.4

Note: The values of 773 K have been interpolated.

24/05/2013 CP 105 CHAPTER 4 28
 From Table D.2
C1 ≡ CH4 , C2 ≡ C2 H6 , etc.

Note: The value of 773 K has been interpolated.

Therefore;
∆𝐇𝐏 = 𝟏 𝟐𝟒, 𝟎𝟏𝟒 − 𝟖𝟕𝟗 + 𝟐 𝟏𝟕, 𝟕𝟗𝟓 − 𝟖𝟑𝟕 = 𝟓𝟕. 𝟎𝟓𝟏 𝐤𝐉
∆𝐇𝐑 = 𝟏 𝟐𝟐, 𝟑𝟒𝟓 − 𝟗𝟏𝟐 + 𝟒 𝟏𝟒, 𝟔𝟏𝟓 − 𝟕𝟏𝟖 = 𝟕𝟕. 𝟎𝟐𝟏 𝐤𝐉
24/05/2013 CP 105 CHAPTER 4 29
 𝐨
∆𝐇𝐫𝐱𝐧, 𝐓 = ∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
+ ∆𝐇𝐏 − ∆𝐇𝐑

= −𝟏𝟔𝟓 + 𝟓𝟕. 𝟎𝟓𝟏 − 𝟕𝟕. 𝟎𝟐𝟏

𝐤𝐉
∴ ∆𝐇𝐫𝐱𝐧, 𝐓 = −𝟏𝟖𝟒. 𝟗𝟖
𝐦𝐨𝐥. 𝐂𝐎𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝
Therefore;
𝐤𝐉
𝐐 = ∆𝐇𝐫𝐱𝐧, 𝐓 = −𝟏𝟖𝟒. 𝟗𝟖
𝐦𝐨𝐥. 𝐂𝐎𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝
𝐤𝐉
∴ 𝐐 = −𝟏𝟖𝟒. 𝟗𝟖
𝐦𝐨𝐥. 𝐂𝐎𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝
The two results appear to be slightly different, this is due
to the estimates of the Enthalpies.
24/05/2013 CP 105 CHAPTER 4 30
  Example 4.14
CO at 50℉ is completely burned at 1 atm pressure with
50% excess air that is at 1000℉. The products of the
combustion leave the combustion chamber at 800℉ .
Calculate the heat evolved from the combustion chamber
expressed as Btu/1bmol of CO entering.
Basis:
Q
1lbmol of CO fed.
CO2 = ?
CO = 1 lbmol. Combustion 800℉
O2 = ?
50℉ = 510°R chamber = 1260°R N2 = ?
50% excess air, Air = ?
1000℉ O2: 21%
= 1460°R N2: 79%
24/05/2013 CP 105 CHAPTER 4 31
 First, the necessary material balances have to be done:
𝟏
Reaction: 𝐂𝐎 + 𝐎𝟐 → 𝐂𝐎𝟐
𝟐
𝐂𝐎 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = 𝟏 𝐥𝐛𝐦𝐨𝐥.
𝟏𝐥𝐛𝐦𝐨𝐥. 𝐂𝐎 𝟏 𝐥𝐛𝐦𝐨𝐥. 𝐂𝐎𝟐
𝐂𝐎𝟐 𝐩𝐫𝐨𝐝𝐮𝐜𝐞𝐝 = = 𝟏 𝐥𝐛𝐦𝐨𝐥. 𝐂𝐎𝟐
𝟏 𝐥𝐛𝐦𝐨𝐥. 𝐂𝐎
𝟏𝐥𝐛𝐦𝐨𝐥. 𝐂𝐎 𝟎. 𝟓 𝐥𝐛𝐦𝐨𝐥. 𝐎𝟐
𝐎𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = = 𝟎. 𝟓 𝐥𝐛𝐦𝐨𝐥. 𝐎𝟐
𝟏 𝐥𝐛𝐦𝐨𝐥. 𝐂𝐎
Theoretical 𝐎𝟐 = 𝐎𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = 𝟎. 𝟓 𝐥𝐛𝐦𝐨𝐥. 𝐎𝟐
𝐎𝟐 𝐬𝐮𝐩𝐩𝐥𝐢𝐞𝐝 = 𝟎. 𝟓 + 𝟏 𝟎. 𝟓 = 𝟎. 𝟕𝟓 𝐥𝐛𝐦𝐨𝐥. 𝐎𝟐
24/05/2013 CP 105 CHAPTER 4 32
 𝟎. 𝟕𝟓 𝐥𝐛𝐦𝐨𝐥. 𝐎𝟐 𝟕𝟗 𝐥𝐛𝐦𝐨𝐥. 𝐍𝟐
𝐍𝟐 𝐬𝐮𝐩𝐩𝐥𝐢𝐞𝐝 = = 𝟐. 𝟖𝟐 𝐥𝐛𝐦𝐨𝐥. 𝐍𝟐
𝟐𝟏 𝐥𝐛𝐦𝐨𝐥. 𝐎𝟐

𝟎. 𝟕𝟓 𝐥𝐛𝐦𝐨𝐥. 𝐎𝟐 𝟏𝟎𝟎 𝐥𝐛𝐦𝐨𝐥. 𝐀𝐢𝐫

𝐀𝐢𝐫 𝐬𝐮𝐩𝐩𝐥𝐢𝐞𝐝 = =𝟑. 𝟓𝟕 𝐥𝐛𝐦𝐨𝐥. 𝐀𝐢𝐫
𝟐𝟏 𝐥𝐛𝐦𝐨𝐥. 𝐎𝟐

𝐎𝟐 𝐮𝐧𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = 𝐎𝟐 𝐬𝐮𝐩𝐩𝐥𝐢𝐞𝐝 − 𝐎𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝

= 𝟎. 𝟕𝟓 − 𝟎. 𝟓 = 𝟎. 𝟐𝟓 𝐥𝐛𝐦𝐨𝐥. 𝐎𝟐

Thus, this is how the block diagram presentation of this

problem now looks like:

24/05/2013 CP 105 CHAPTER 4 33

 Q
CO2 = 1 lbmol
CO = 1 lbmol. Combustion 800℉
O2 = 0.25 lbmol.
50℉ = 510°R chamber = 1260°R
N2 = 2.82 lbmol.
50% excess air, A = 3.57 lbmol.
1000℉ O2: 21% = 0.75 lbmol.
= 1460°R N2: 79% = 2.82 lbmol.

After doing material balances, the second step is to do

energy balances:
24/05/2013 CP 105 CHAPTER 4 34
  Recall the energy balance equation for open system:
^ ^ ^
∆𝐄 = −∆ 𝐦 𝐇 + 𝐊 + 𝐏 + 𝐐 − 𝐖
Simplifications of the energy balance equation;
a steady state process: ΔE = 0
no potential and kinetic energies: ΔP = 0, ΔK = 0,
no mechanical movements of the system: W = 0.
Thus, the energy balance equation can be reduced to:
^
𝐐 = 𝐦. ∆𝐇 = ∆𝐇 = ∆𝐇𝐫𝐱𝐧,𝐓
𝐨
∆𝐇𝐫𝐱𝐧, 𝐓 = ∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
+ ∆𝐇𝐏 − ∆𝐇𝐑
24/05/2013 CP 105 CHAPTER 4 35
 𝐨 ^𝐨 ^ 𝐨
∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
= 𝐧𝐢 𝐇𝐟,𝐢 − 𝐧𝐢 𝐇𝐟,𝐢
𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐬 𝐑𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬

^𝐨 ^𝐨 ^
𝐨 𝐨
∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
= 𝐧𝐂𝐎𝟐 ∆𝐇𝐟,𝐂𝐎𝟐 − 𝐧𝐂𝐎 ∆𝐇𝐟,𝐂𝐎 + 𝐧𝐎𝟐 ∆𝐇𝐟,𝐎 𝟐

From Table F.1 (appendix F), David Himmelblau’s book:

^ ^𝐨
𝐨 ∆𝐇𝐟,𝐎𝟐 = 𝟎 𝐤𝐉/𝐠𝐦𝐨𝐥,
∆𝐇𝐟,𝐂𝐎 = −𝟏𝟏𝟎. 𝟓𝟐 𝐤𝐉/𝐠𝐦𝐨𝐥,
^𝐨
∆𝐇𝐟,𝐂𝐎𝟐 = −𝟑𝟗𝟑. 𝟓𝟏 𝐤𝐉/𝐠𝐦𝐨𝐥

𝐓𝐫𝐞𝐟 = 𝟐𝟓℃ = 𝟕𝟕℉ = 𝟓𝟑𝟕°𝐑

24/05/2013 CP 105 CHAPTER 4 36
 𝐨
∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
= 𝟏 −𝟑𝟗𝟑. 𝟓𝟏 − 𝟏 −𝟏𝟏𝟎. 𝟓𝟐 + 𝟎. 𝟓 𝟎

𝐨 𝐤𝐉
∴ ∆𝐇𝐫𝐱𝐧,𝐓 = −𝟐𝟖𝟗. 𝟗𝟗
𝐫𝐞𝐟
𝐠𝐦𝐨𝐥. 𝐂𝐎

𝐨 −𝟐𝟖𝟗. 𝟗𝟗 𝐤𝐉 𝟏 𝐁𝐭𝐮 𝟒𝟓𝟒 𝐠𝐦𝐨𝐥

∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
=
𝐠𝐦𝐨𝐥. 𝐂𝐎 𝟏. 𝟎𝟓𝟓 𝐤𝐉 𝟏 𝐥𝐛𝐦𝐨𝐥

𝐨 𝐁𝐭𝐮
∴ ∆𝐇𝐫𝐱𝐧,𝐓 = −𝟏𝟐𝟒, 𝟕𝟗𝟏. 𝟗𝟎𝟓
𝐫𝐞𝐟
𝐥𝐛𝐦𝐨𝐥. 𝐂𝐎

24/05/2013 CP 105 CHAPTER 4 37

 ^ ^
∆𝐇𝐏 = 𝐧𝐢 𝐇𝐢,𝐓𝐨 − 𝐇𝐢,𝐓𝐫𝐞𝐟
𝐏𝐫𝐨𝐝𝐮𝐜𝐭𝐬
^ ^ ^ ^
∆𝐇𝐏 = 𝐧𝐂𝐎𝟐 𝐇𝐂𝐎𝟐 ,𝟖𝟎𝟎℉ − 𝐇𝐂𝐎𝟐 ,𝟕𝟕℉ + 𝐧𝐎𝟐 𝐇𝐎𝟐 ,𝟖𝟎𝟎℉ − 𝐇𝐎𝟐 ,𝟕𝟕℉
^ ^
+𝐧𝐍𝟐 𝐇𝐍𝟐,𝟖𝟎𝟎℉ − 𝐇𝐍𝟐,𝟕𝟕℉
^ ^
∆𝐇𝐑 = 𝐧𝐢 𝐇𝐢,𝐓𝐢𝐧 − 𝐇𝐢,𝐓𝐫𝐞𝐟
𝐑𝐞𝐚𝐜𝐭𝐚𝐜𝐭𝐬
^ ^ ^ ^
∆𝐇𝐑 = 𝐧𝐂𝐎 𝐇𝐂𝐎,𝟓𝟎℉ − 𝐇𝐂𝐎,𝟕𝟕℉ +𝐧𝐀𝐢𝐫 𝐇𝐀𝐢𝐫,𝟏𝟎𝟎𝟎℉ − 𝐇𝐀𝐢𝐫,𝟕𝟕℉
Enthalpies of various gases are taken from Table 4.3 (page
390 David Himmelblau’s book) or Table 4.4A in Btu/lbmol.
24/05/2013 CP 105 CHAPTER 4 38
 ∆𝐇𝐏 = 𝟏 𝟖𝟎𝟐𝟔 − 𝟑𝟗𝟐. 𝟐 + 𝟎. 𝟐𝟓 𝟓𝟔𝟗𝟎 − 𝟑𝟏𝟓. 𝟏 +
𝟐. 𝟖𝟐 𝟓𝟒𝟒𝟑 − 𝟑𝟏𝟑. 𝟐
𝐁𝐭𝐮
∴ ∆𝐇𝐏 = 𝟐𝟑, 𝟒𝟒𝟑. 𝟓𝟔𝟏
𝐥𝐛𝐦𝐨𝐥. 𝐂𝐎
∆𝐇𝐑 = 𝟏 𝟏𝟐𝟓. 𝟐 − 𝟑𝟏𝟑. 𝟑 + 𝟑. 𝟓𝟕 𝟔𝟗𝟖𝟒 − 𝟑𝟏𝟐. 𝟕
𝐁𝐭𝐮
∴ ∆𝐇𝐑 = 𝟐𝟑, 𝟔𝟐𝟖. 𝟒𝟒𝟏
𝐥𝐛𝐦𝐨𝐥. 𝐂𝐎
24/05/2013 CP 105 CHAPTER 4 39
 Therefore;
𝐨
∆𝐇𝐫𝐱𝐧,𝐓 = ∆𝐇𝐫𝐱𝐧,𝐓𝐫𝐞𝐟
+ ∆𝐇𝐏 − ∆𝐇𝐑

= −𝟏𝟐𝟒, 𝟕𝟗𝟏. 𝟗𝟎𝟓 + 𝟐𝟑, 𝟒𝟒𝟑. 𝟓𝟔𝟏 − 𝟐𝟑, 𝟔𝟐𝟖. 𝟒𝟒𝟏

𝐁𝐭𝐮
∴ ∆𝐇𝐫𝐱𝐧,𝐓 = −𝟏𝟐𝟒, 𝟗𝟕𝟔. 𝟕𝟖𝟓
𝐥𝐛𝐦𝐨. 𝐂𝐎
Therefore;
𝐁𝐭𝐮
𝐐 = ∆𝐇𝐫𝐱𝐧,𝐓 = −𝟏𝟐𝟒, 𝟗𝟕𝟔. 𝟕𝟖𝟓
𝐥𝐛𝐦𝐨. 𝐂𝐎
𝐁𝐭𝐮
∴ 𝐐 = −𝟏𝟐𝟒, 𝟗𝟕𝟔. 𝟕𝟖𝟓
𝐥𝐛𝐦𝐨𝐥. 𝐂𝐎
24/05/2013 CP 105 CHAPTER 4 40
 It can be noted that all of the process streams (reactants
and products) refer to a reference temperature of 77℉
25℃ .

The reference temperature could have been 50℉. But it

is difficult to get the standard heats of formation at this
reference temperature. Hence the evaluation of
𝐨
∆𝐇𝐫𝐱𝐧,𝟓𝟎℉ would become very difficult.

24/05/2013 CP 105 CHAPTER 4 41