MODULE 2 - HEAT EFFECTS II

STANDARD HEAT OF REACTION

Consider the flow calorimeter method for measurement of heats of combustion of a fuel.

1. The fuel is combined with air and flows into a combustion chamber.
2. The combustion products enter a water jacketed section in which they are cooled to the
temperature of the reactants.

So there is a heat flowing from the calorimeter and absorbed by the water which is equal to Q.

Energy Balance:
1
䷀ٛ ∆H + u2 + zg
2
Neglecting the shaft work, the kinetic and potential energy,

Thus, the heat exchanged is equal to the enthalpy change caused by chemical reaction and this enthalpy
change of reaction is called the heat of reaction.

The standard heat of reaction is defined as the enthalpy change when the reactants in their standard
states is react to form products in their standard states at the same temperature T.

The standard state is the form which it is most stable at 25°C and 1 bar. For example the standard state of
Carbon is solid at 25°C and 1 bar and we specify this by writing th.

Consider this thermochemical equation synthesis of ammoniah.

1 °
2 2 +2 2 ∆ 2䷀ٛ
䷀ at,11d

When a heat of reaction is given, it applies for the stoichiometric coefficients as written.
°
If each stoichiometric coefficient is doubled, the ∆ is doubled.
°
2 + 2 2 ∆ 2䷀ٛ
2 ䷀ at,11d ䷀ ䷀2,22d

If the equation is written in reverse, the heat of reaction changes only in sign.
1 °
2 + 2 ∆ 2䷀ٛ
at,11d
2 2

STANDARD HEAT OF FORMATION

Formation reaction is the reaction which forms a single compound from its constituent elements.

Example:

th + 2 2

1
2 +2 2 2 h
In calculations related to enthalpy changes for reactions at standard states, this follows the Hess's Law
where it states that it is permissible to write thermochemical equations together with the enthalpy
change and to treat as mathematical equations to obtain a themochemically valid result.

Example 1
Calculate the standard heat at 25°C for the following reaction.

a + 2 2 2 +2 2

GIVEN:
° °
From Perry’s CHE Handbook: ∆ 2䷀ٛ
䷀ ䷀2, dǣ ∆ 2䷀ٛ 2 ䷀ 2a1,ٛ1ٛ

SOLUTION:
1 1 °
2 + 2 ∆ 2䷀ٛ
䷀ ䷀2, dǣ
2 2

1 °
2 +2 2 2 ∆ 2䷀ٛ
䷀ 2a1,ٛ1ٛ

By Hess's Law, we can calculate the heat of reaction by this manner.

°
a 2 2 +2 2 ∆ 2䷀ٛ
a ䷀2, dǣ h

°
2 2 + 2 2 2 ∆ 2䷀ٛ
2 ䷀ 2a1,ٛ1ٛ

°
a + 2 2 2 +2 2 ∆ 2䷀ٛ
䷀ 11a,adٛ

STANDARD HEAT OF COMBUSTION

Combustion reaction is defined as a reaction between an element or compound and oxygen to form
specified combustion products.

C s + O2 g CO2 g ∆H ䷀ ䷀ ,5d䷀ J

1
2 +2 2 2 ∆ ䷀ 2ٛ5,ٛ d

A reaction such as the formation of n-butane: aC sh +5H2 gh → CaH1d gh is not feasible in practice.
However, this equation results from combination of the following combustion reactions:

aC sh + aO2 gh → aCO2 gh ΔH2䷀ٛ ° ah ䷀ ䷀ ,5d䷀h

5H2 gh + 1/2 O2 gh → 5H2O lh ΔH2䷀ٛ ° 5h ䷀2ٛ5,ٛ dh

aCO2 gh + 5H2O lh → CaH1d gh + 1 /2 O2 gh ΔH2䷀ٛ° 2,ٛǣǣ, ䷀t

aC sh + 5H2 gh → CaH1d gh ΔH2䷀ٛ ° ䷀125,ǣ䷀d J

TEMPERATURE DEPENDENCE OF ΔH

°
∆

This formula also defines the standard heat of reaction where is the stoichiometric numbers of
each chemical specie signed stoichiometric coefficient positive for products, and negative for
reactantsh.

From the knowledge of the value at standard state, we can calculate the heats of reaction at other
temperature.

The fundamental equation relating heats of reaction to temperature:

°
°
∆
∆ ∆ d
+t
t t

T C po B 2 2 C 3 3 D    1 

To R
dT  ATo (  1) 
2
To (  1) 
3
To (  1)  
To   


T

  A  B(T )  C (T 2 )  D(T  2 ) dT
To

where ∆ B   vi Bi C   vi Ci D   vi Di

∆C°p ∆B ∆C 2 2 ∆D
H
∆A + To τ + 1h + To τ + τ + 1h +
R 2 τTo2

Example 2
Calculate the standard heat of the methanol-synthesis reaction at ٛdd°C:

CO g + 2H2 g CH OH g

GIVEN:

1dǣ .15
To 2䷀ٛ.15 K T 1dǣ .15 K τ
2䷀ٛ.15

∆H°o vi∆Hfi ䷀ 2dd,ttd J + ䷀ 1 ䷀ 11d,525 Jh ䷀ ䷀d,1 5 J

SOLUTION:

i 1d 1dt 1d䷀5
1 2.211 12.21t - .a5d d
-1 . ǣt d.55ǣ d -d.d 1
2 -2 .2a䷀ d.a22 d d.dٛ
 ∆A 1 2.211 + ䷀ 1 . ǣt + ䷀ 2 .2a䷀ ䷀ ǣ.tt

∆B 1 12.21tx1d䷀ + ䷀ 1 d.55ǣx1d䷀ + ䷀ 2 d.a22x1d䷀ 1d.ٛ15x1d䷀

∆C ䷀ .a5dx1d䷀t

∆D ䷀ 1 ䷀ d.d 1x1d5 + ䷀ 2 d.dٛ x1d5 ䷀ d.1 5x1d5

T ∆C°p 1dǣ .15 1d.ٛ15x1d䷀ 2

1dǣ .15 2
dT ䷀ ǣ.tt 2䷀ٛ.15 ䷀1 + 2䷀ٛ.15 ䷀1
To R 2䷀ٛ.15 2 2䷀ٛ.15
1dǣ .15
䷀ .a5dx1d䷀t 1dǣ .15 ䷀ d.1 5x1d5 ䷀1
+ 2䷀ٛ.15 ䷀1 + 2䷀ٛ.15
2䷀ٛ.15 2䷀ٛ.15 1dǣ .15
2䷀ٛ.15
䷀ 1t15.5K

∆ ䷀ , + . ䷀ . ䷀ ,

Example
Calculate the enthalpy of reaction at 2䷀ٛ K for the following reaction:

H2 O g + CH OH g CO2 g + H2 g

GIVEN:

i vi ΔH
H2O -1 -2a1.ٛ2 kJ/mol
CH OH -1 -2dd.tt kJ/mol
CO2 1 - ䷀ .51 kJ/mol
H2 d

SOLUTION:

∆H°o vi ∆Hfi ䷀ ䷀ .51 1 + d + ䷀ 1 ䷀ 2a1.ٛ2 + ䷀ 1 ䷀ 2dd.tt a䷀ kJ mol䷀1

Example a
°
Estimate ∆ 2䷀ٛ
for acetylene as a liquid at 25°C.

SOLUTION:

Given: Tc dٛ. K Pc t1. ䷀ bar Tn 1ٛ䷀.a K T 2䷀ٛ.15 K

Trn Tn/Tc d.t1a Tr T/Tc d.䷀tǣ

 ln Pc  1.013 
H n  1.092 RTn    16.91kJ / mol
 0.930  Trn 
 0.38
 1  Tr 
H v  H n    6.638kJ / mol
 1  Trn 

ΔHf 22ǣ.aٛ kJ/mol

∆H°f2䷀ٛ ΔHf - ΔHv 22ǣ.aٛ - t.t ٛ kJ/mol 22d.ٛa2 kJ/mol

°
PROBLEM 1: Estimate ∆ 2䷀ٛ
for ethylbenze and n-hexane as a liquid at 25°C.

HEAT EFFECTS OF INDUSTRIAL REACTIONS

Industrial Reactions

 rarely carried out under standard state conditions

 reactants may not be present in stoichiometric proportions
 reaction may not go to completion
 the final temperature may differ from the initial temperature

Example 5
What is the maximum temperature that can be reached by the combustion of methane with 2d%
excess air? Both the methane and the air enter the burner at 25°C.

GIVEN: a +2 2 2 + 2 ∆ ䷀ ٛd2,t25

SOLUTION:

Because the problem is to find the maximum temperature, assume that there is no heat loss in the
system.
° °
d ∆ 2䷀ٛ
䷀∆ d

° °
∆ 2䷀ٛ
∆

ΔH
°
∆ enthalpy at
products streamh

°
∆ 2䷀ٛ
 AIR
STACK GAS
BURNER
FUEL: CHa

Basis: 1mol CHa

Reactants:

a
1 t

2
䇅 t 䇅䇅 2 + 䇅 tt 2 2 1 + d.2 2.a t

ǣ䷀ t t 2
2.a t t 2 ䷀.d t
2
21 t t 2

Stack gases Combustion Productsh:

2
1 t

2
2 t

2
䇅 tt 2 d.a t

2 2 t ䷀.d t

∆ ٛd2,t25 ䷀ 2䷀ٛ.15

+ t +1 + t2 2 + +1 +
2 t2

1 5.a5ǣ + 2 .aǣd + d.a .t ䷀ + ䷀.d .2ٛd a .aǣ1

1 1.da5 1d䷀ + 2 1.a5d 1d䷀ + d.a d.5dt 1d䷀ + ䷀.d .2ٛd 1d䷀ ䷀.5d2 1d䷀

1 ䷀ 1.15ǣ 1d5 + 2 d.121 1d5 + d.a d.5dt 1d5 + ䷀.d d.dad 1d5 ䷀ d.ta5 1d5

ٛd2,t25
+ 2䷀ٛ.15
d.ta5 1d5
ٛ. 1aah a .aǣ1 + a.ǣ51 1d䷀ + 2䷀ٛ.15 ䷀
2䷀ٛ.15
Let T > 2䷀ٛ.15 Use numerical methodh

1. tdd 2 5.ǣdad
 2. 2 5.ǣdad 2d25. 1 ٛ
. 2d25. 1 ٛ 2dǣ2.5ٛ15
a. 2dǣ2.5ٛ15 2dt5.2dٛ1
5. 2dt5.2dٛ1 2dtt. 5ad
t. 2dtt. 5ad 2dtt.1ǣ5ٛ
ǣ. 2dtt.1ǣ5ٛ 2dtt.2d 5
ٛ. 2dtt.2d 5 2dtt.1䷀䷀2
䷀. 2dtt.1䷀䷀2 2dtt.1䷀䷀䷀
1d. 2dtt.1䷀䷀䷀ 2dtt.1䷀䷀ٛ
11. 2dtt.1䷀䷀ٛ 2dtt.1䷀䷀ٛ

Final Answer: 2dtt.1䷀䷀ٛ K

PROBLEM 2: Calculate the theoretical flame temperature when ethylene at 25°C is burned with:
ah The theoretical amount of air at 25°C.

bh 25% excess air at 25°C.

Example t
A boiler is fired with a high-grade fuel oil (consisting only of hydrocarbons) having a standard heat of
combustion of -43,515 J/g at 25°C with 2 and 2 as products. The temperature of the fuel
and air entering the combustion chamber is 25°C. The air is assumed dry. The flue gases leave at
300°C, and their average analysis (on a dry basis) is 11.2% 2 , 0.4% , 6.2% 2 , and 82.2% 2 .
Calculate the fraction of the heat of combustion of the the oil that is transferred as heat to the boiler.

AIR
STACK GAS
BURNER
FUEL 11.2% 2

d.a%

t.2% 2

ٛ2.2% 2
This problem is a combustion calculation based on the flue gas analysis, so we have to find the
empirical formula of the fuel, and the kilogram of fuel used to calculae the fraction of the heat of
combustion that is generated to the boiler. Since the given is based on the mole percent, then we have
the basis of 100 moles of dry stack gas for convenience.

Basis of 100 mol DSG

21
O2 from air ٛ2.2 21.ٛ5
ǣ䷀
O2 balance (This is used to find the moles of oxygen unaccounted, and the moles H2O formed from
combustion)

d.a
O2 unaccounted for 21.ٛ5 ䷀ 11.2 ䷀ ䷀ t.2 ٛ.5 moles H2 O
2
H2 balance

moles H2 O from the fuel ٛ.5

C balance

moles CO2 + moles CO moles C in the fuel

11.2 + d.a 11.t moles C

2kg H2 12kg C
mass of fuel burned ٛ.5 + 11.t
mole mole
° ䷀1
∆ 2䷀ٛ
䷀ a ,515 15t.2 ䷀ tǣ䷀ǣdad

°
This value of ∆ 2䷀ٛ
must be the heating value of the fuel, but according to the problem based on the
flue gas analysis, the combustion is incomplete due to presence of CO in the flue gas, and H2O is formed
as vapor than as liquid, thus this represents a loss of heat.

ΔH
°
∆

°
∆ 2䷀ٛ

This is the hypothetical path for calculation of enthalpy.

To find the heat tranferred to the boiler, first make an combustion reaction of the fuel actualh where its
empirical formula is C11.tH1ǣ.

C11.t H1ǣ l + 15.t5O2 11.2CO2 g + d.aCO g + ٛ.5H2 O g

The heat of combustion of the given reaction above is obtained by following the Hess's rule with the
following reactions for which the ∆ °2䷀ٛ is known.
C11.t H1ǣ l + 15.t5O2 11.tCO2 g + ٛ.5H2 O g ΔH -tǣ䷀ǣdad J

ٛ.5H2 l ٛ.5H2 O g ΔH aa.d12 ٛ.5h J

d.aCO2 g d.aCO g + d..2O2 g ΔH 2ٛ2.䷀ٛa d.ah J

After calculating the heat of combustion at standard state, calculate the enthalpy at the products stream
since flue gas leave at dd°C due to the flame temperature.

° 5ǣ .15 ䷀ 2䷀ٛ.15
∆

+ t + 1h + t2 2
+ + 1h +
t 2 t2

Combustion n in molh A 1d B 1dtC 1d-5D CP/R

products
CO2 11.2 5.a5ǣ 1.da5 d -1.15ǣ 5.2 52
CO d.a . ǣt d.55ǣ d -d.d 1 .tdd5
H2O ٛ.5 .aǣd 1.a5d d d.121 a.1ǣ25
O2 t.2 .t ䷀ d.5dt d -d.22ǣ .ǣ2tǣ
N2 ٛ2.2 .2ٛd d.5䷀5 d d.dad .5t1ٛ

∆ ٛ. 1a 11.2 5.2 52 + d.a .tdd5 + ٛ.5 a.1ǣ25 + t.2 .ǣ2tǣ + ٛ2.2 .5t1ٛ 5ǣ .15
䷀ 2䷀ٛ.15 ䷀adttd

∆ ䷀ t d䷀ǣad + ䷀adttd ䷀ 5 t䷀dٛd

5 t䷀dٛd
1dd ǣ䷀%
tǣ䷀ǣdad
Final Answer: ǣ䷀%

PROBLEM : What is the standard heat of combustion of n-pentane gas at 25°C if the combustion
products are H2O lh and CO2 gh?
PROBLEM a: Determine the standard heat of each following reactions at 25°C:
ah N2 gh + H2 gh → 2NH gh

bh aNH gh + 5O2 gh → aNO gh + tH2O gh

ch NO2 gh + H2O lh → 2HNO lh + NO gh

dh CaC2 gh + H2O lh → C2H2 gh + CaO sh

eh 2Na sh + 2H2O lh → 2NaOH sh + H2 gh

Prepared by:
Engr. Reggie A. Dueňas
Instructor I