BALANCE ON REACTIVE PROCESSES

The heat of reaction (or enthalpy of reaction)  H r (T,P)

enthalpy change for a process in which stoichiometric quantities of reactants at
temperature T and pressure P react completely in a single reaction to form products
at the same T and P.

means that the enthalpy change for the given reaction is:

if 150 mol of C/s was generated in the given reaction at 100°C and 1 atm:

More generally: (nA,r moles of A are consumed)

Vi: (+) for product and (-) for reactant

Since extent of reaction:

if a reaction takes place at a temperature To and pressure Po and the extent of reaction is ξ, the
associated enthalpy change is; 
H   . H r (T0 , P0 ) 1
1) If ∆Hr (T, P) is negative the reaction is exothermic at temperature T and pressure P,
If ∆Hr (T, P) is positive the reaction is endothermic at T and P.
2) At low and moderate pressures, ∆Hr (T, P) is nearly independent of P.
3) The value of the heat of a reaction depends on how the stoichiometric equation is
written

4) The value of a heat of reaction depends on the states of aggregation (gas, liquid, or
solid) of the reactants and products.


difference between the heats of reactions is heats of vaporization of water: 2. H v(25 0 C )

 0
5) The standard heat of reaction  H r is the heat of reaction when both the reactants
and products are at a specified reference T and P, usually (and always in this course)
25°C and 1 atm.

2
If a reaction takes place in a closed reactor at constant volume:
the heat released or absorbed is determined by the change in internal energy
between reactants and products

The internal energy of reaction,  U r (T ) (Uproducts – Ureactants)

 
   
 U r (T )   H r (T )  RT   vi   vi 
 gaseous gaseous 
 products reac tan ts 

including only gaseous reactants

and products

3
MEASUREMENT AND CALCULATION OF HEAT OF REACTION: HESS'S LAW
A heat of reaction may be measured in a calorimeter-a closed reactor immersed in
a fluid contained in a well-insulated vessel. The rise or fall of the fluid temperature
can be measured and used to0 determine the energy released or absorbed by the

reaction, and the value of  H r may then be calculated from that energy and
known reactant and product heat capacities. There are serious limitations to this
 0
technique, however. Suppose, for example, you wish to determine  H r for the
reaction

You could put 1 mole of carbon and 0.5 mole of oxygen together in a reactor,
but you would never get 1 mole of carbon monoxide as the final product. If the
reactants are at or near 25°C or lower, nothing apparent would occur since the
rate at which carbon and oxygen react at this temperature is immeasurably low.
If, on the other hand, the mixture were heated to a temperature at which C and
O2 react at a measurable rate, the product would be either pure CO2 or at best
a mixture of CO and CO2, making it impossible to determine the heat of the
CO formation reaction alone.

4
 MEASUREMENT AND CALCULATION OF HEAT OF REACTION: HESS'S LAW

If the equation for reaction 2

is subtracted from that for reaction 1,
the result is

Hess's law: If the stoichiometric equation for reaction 1 can be obtained by algebraic
operations (multiplication by constants, addition, and subtraction) on stoichiometric
equations for reactions 2,3, ... , then the heats of reaction of 1 can be obtained by
performing the same operations on the heats of reactions 2 and 3 .... 5
FORMATION REACTIONS AND HEATS OF FORMATION

 0  0  0  0
 H r   vi H fi   vi  H fi   vi  H fi
i products reac tan ts
6
7
APEx codes:

8
mol
mol
mol
mol

9
FORMATION REACTIONS AND HEATS OF FORMATION

Heats of formation at any T:

T
H Tf  H 0f   C p .dT
25

10
 HEATS OF COMBUSTION

Standard heats of reactions that involve only combustible substances and

combustion products can be calculated from tabulated standard heats of
combustion 
 0  0  0  0
 H r   vi ( H c )i   vi  ( H c )i   vi ( H )
c i
i reac tan ts products
11
minus!
Example 9.4-1: Calculation of a Heat of Reaction from Heats of Combustion

1 molx 1 molx 1 molx

If there is no heats of formation data we can use heats of combustion data

12
molmol

13
ENERGY BALANCE ON REACTIVE PROCESSES
Heats of Reaction Method:
This 0method is generally preferable when there is a single reaction for which

Hr is known

Example: Calculate cooling or heating rate (Q) of furnace

(kJ/s)

Since it is fed as mol/s

14
1. Complete the material balance calculations on the reactor to the greatest extent possible

15
2. Choose reference states for specific enthalpy calculations
The best choices are generally reactant and product species at 25°C and 1 atm in the
states for which the heat of reaction is known:
[C3H8(g), O2(g), CO2(g), and H20(l) in the example process]
and nonreacting species at any convenient temperature, such as the reactor inlet or
outlet temperature or the reference condition used for the species in an available
enthalpy table

16
3. For a single reaction in a continuous process, calculate the extent of reaction

mol

17
4. Prepare the inlet-outlet enthalpy table, inserting known molar amounts (ni) or flow rates
(ni) for all inlet and outlet stream components.

Since C3H8 is in its reference state: H1=0

18
 5. Calculate each unknown stream component enthalpy, Hi as ∆H for the species going from
its reference state to the process state, and insert the enthalpies in the table.
T2
b 2 c 3 d 4
T 1        
2 3 4
if Cp  a  bT  cT  dT 2 3
Cp.dT a (T2 T1 ) (T2 T1 ) (T2 T1 ) (T2 T1 )
2 3 4
300
 1,158.10 5 0,6076.10 8 1,311.10 12
H 2   CpO2 ( g ) .dT  29,1.10 (300  25) 
3
(300  25 ) 
2 2
(300  25 ) 
3 3
(300 4  254 )
25
2 3 4

300
 0,2199.105 0,5723.10 8 2,871.10 12
H 3   CpN 2 ( g ) .dT  29.10 (300  25) 
3
(300  25 ) 
2 2
(300  25 ) 
3 3
(3004  254 )
25
2 3 4

1000
 1,158.10 5 0,6076.10 8 1,311.10 12
H4  
25
CpO2 ( g ) .dT  29,1.10 3 (1000  25) 
2
(10002  252 ) 
3
(10003  253 ) 
4
(10004  254 )

19
 0,2199.10 5 0,5723.10 8 2,871.10 12
 1000


3
H5  CpN 2 ( g ) .dT  29.10 (1000  25)  (1000  25 ) 
2 2
(1000  25 ) 
3 3
(1000 4  254 )
25
2 3 4

4,233.10 5 2,887.10 8 7,464.10 12

 1000
H6  
25
CpCO2 ( g ) .dT  36,11.10 3 (1000  25) 
2
(1000 2  252 ) 
3
(10003  253 ) 
4
(1000 4  254 )

 100 1000
H7   Cp .dT  HV (100 C )   CpH 2O ( v ) .dT
o
H 2O (l )
25 100

100

25
 CpH 2O 2 (l ) .dT  75,4.10 3 (100  25)

∆HV(100oC)=40.656 kJ/mol (T.B.1)

1000
0,6880.10 5 0,7604.10 8 3,593.10 12
100 CpH 2O( g ) .dT  33,46.10 (1000  100) 
3
(1000  100 ) 
2 2
(1000  100 ) 
3 3
(10004  1004 )
2 3 4

20
CpN 2 ( g )  29.10 3  0,2199.105 T  0,5723.108 T 2  2,871.10 12 T 3 (kJ / mol.o C )

CpO2 ( g )  29,1.10 3  1,158.10 5 T  0,6076.10 8 T 2  1,311.10 12 T 3 (kJ / mol.o C )

CpCO2 ( g )  36,11.10 3  4,233.10 5 T  2,887.10 8 T 2  7,464.10 12 T 3 (kJ / mol.o C )

CpH 2O( g )  33,46.10 3  0,6880.10 5 T  0,7604.10 8 T 2  3,593.10 12 T 3 (kJ / mol.o C )

CpH 2O( l )  75,4.10 3 (kJ / mol.o C )

21
6. Calculate ∆H for the reactor Use one of the following formula:

  0  
 H   . H r   nout H out   nin H in Single reaction
  0  
 H    j . H r j   nout H out   nin H in Multiple reactions

∆H=100.(-2220)+[(100.32,47)+(2256.30,56)+(300.48,60)+(400.81,71)] –
[(600.8,47)+(2256.8,12)]

Since ΔH is negative heat is generated!

Since Q = ΔH then Q= -1.26x105 kJ/s furnace is cooling!

22
Heat of Formation Method:

This method is generally preferable for multiple reactions and single reactions for which
 0
Hr is not readily available

1. Complete the material balance calculations on the reactor to the greatest extent possible.

2. Choose reference states for enthalpy calculations.

(This is the step that distinguishes the preceding method from this one.) The
choices should be the elemental species that constitute the reactants and products
in the states in which the elements are found at 25°C and 1 atm [C(s), H2(g), etc.]
and nonreacting species at any convenient temperature. In the example, the
reference states would be C(s), H2(g), and O2(g) at 25°C (the elemental
species constituting the reactants and products), and N2 at 25°C (the reference
temperature of Table B.8).

23
24
  300
H 2  H   CpO 2( g ) .dT  8.47kJ / mol
0 There is no heat of formation term
f
for elemental species:
25

300
 1,158.105 0,6076.108 1,311.1012
H 2   CpO2 ( g ) .dT  29,1.10 (300  25) 
3
(300  25 ) 
2 2
(300  25 ) 
3 3
(3004  254 )
25
2 3 4

 300
H 3  H   Cp N 2( g ) .dT  8.12kJ / mol
0
f
25
300
 0,2199.105 0,5723.10 8 2,871.10 12
H 3   CpN 2 ( g ) .dT  29.10 (300  25) 
3
(300  25 ) 
2 2
(300  25 ) 
3 3
(3004  254 )
25
2 3 4

25
  1000
H 4  H   Cp .dT  32.47 kJ / mol
0
f O 2( g )
25
1000
 1,158.10 5 0,6076.10 8 1,311.10 12

3
H4  CpO2 ( g ) .dT  29,1.10 (1000  25)  (1000  25 ) 
2 2
(1000  25 ) 
3 3
(1000 4  254 )
25
2 3 4

 1000
H 5  H   Cp .dT  30.56kJ / mol
0
f N 2( g )
25
1000
 0,2199.10 5 0,5723.10 8 2,871.10 12

3
H5  CpN 2 ( g ) .dT  29.10 (1000  25)  (1000  25 ) 
2 2
(1000  25 ) 
3 3
(1000 4  254 )
25
2 3 4

 1000
H 6  H   Cp .dT  344.9kJ / mol
0
f CO 2 ( g )
25

1000
 4,233.10 5 2,887.10 8 7,464.10 12
H 6  393,5  
25
CpCO2 ( v ) .dT  36,11.10 3 (1000  25) 
2
(10002  252 ) 
3
(10003  253 ) 
4
(10004  254 )

26
  1000
H 7  H   Cp .dT  204.1kJ / mol
0
f H 2O ( v )
25

1000
 0,6880.10 5 0,7604.10 8 3,593.10 12
H 7  241,83  
25
CpH 2O( v ) .dT  33,46.10 3 (1000  25) 
2
(1000 2  25 2 ) 
3
(1000 3  253 ) 
4
(1000 4  25 4 )

  
 H   nout H out   nin H in

[400.(-204,1)+300(-344,9)+30,56.2256+32,47.100] - [100(-103,8)+8,47.600+8,12.2256]
=-1,26x105 kJ/s

27
Heat of Reaction method:

/s

28
Heat of Formation method:

29
THERMOCHEMISTRY OF SOLUTIONS

The enthalpy change associated with the formation of a solution from the
solute elements and the solvent at 25°C is called the standard heat of
formation of the solution.

If a solution contains r moles of solvent per mole of solute;

 o   o   o
  H f     H f    H s (r )
  solution   solute

Heats of formation Heats of formation Heats of solution

of solution = of solute + at 25oC
[kJ/mol solute] [kJ/mol solute] [kJ/mol solute]

30
Example:
Calculate heats of formation of HCI(aq, r=5) solution.

 o   o   o
  H f     H f    H s (r  5)
  HCI ( aq ,r 5)   HCI ( g )

= -92.31 + (- 64.05) = - 156.36 kJ/mol HCI

T.B-1 T.B-11

31
Example 9.5-5:

(tabulated data)

 309 kcal kJ
.   1294 kJ / mol
mol 0.239 kcal

32
 471.9 kcal kJ
.   1974 kJ / mol
mol 0.239 kcal

33
2. If 5.00 mol of NaOH dissolved in 250 mol of water is neutralized completely at 25°C
with dilute phosphoric acid, what is the attendant enthalpy change?

34
FUELS AND COMBUSTION
The use of heat generated by a combustion reaction to produce steam, which drives
turbines to produce electricity, may be the single most important commercial application
of chemical reactions.
The heating value of a combustible material is the negative of the standard heat of
combustion. The higher heating value (or total heating value or gross heating value) is -
∆Hco with H20(l) as a combustion product, and the lower heating value (or net heating
value) is the value Based on H20(v) as a product. Since -∆Hco is always negative the heating
value is positive.

The heat of vaporization of water at 25oC is

If a fuel contains a mixture of combustible substances,its heating value (lower or higher) is

HV=energy/mass and xi=mass fraction

HV=energy/mol and xi=mole fraction
35
Example 9.6-1
Calculation of a Heating Value

A natural gas contains 85% methane and 15% ethane by volume.The heats of combustion
of methane and ethane at 25oC and 1 atm with water vapor as the assumed product are
given below:

Calculate the higher heating value (kJ/g) of the natural gas.

Since the heating value per unit mass of the fuel is desired, we will first calculate the
composition on a mass basis:

Mw=16 g/mol
Mw=30 g/mol

36
The higher heating values of the components are calculated from the given heats of
combustion (which are the negatives of the lower heating values) as follows:

37
Adiabatic Flame Temperature
When a fuel is burned, a considerable amount of energy is released. Some of this energy is
transferred as heat through the reactor walls, and the remainder raises the temperature of
the reaction products; the less heat transferred, the higher the product temperature. The
highest achievable temperature is reached if the reactor is adiabatic and all of the energy
released by The combustion goes to raise the temperature of the combustion products.
This temperature is called the adiabatic flame temperature, Tad.
Suppose nf (mol/s) of a fuel species with heat of combustion ∆Hco is burned completely
with Pure oxygen or air in a continuous adiabatic reactor. If the reference states of the
molecular feed and product species are those used to determine ∆Hco ,the enthalpy
change from inlet to outlet is determined from

Since the reactor is adiabatic, Q=0 in the energy balance. If shaft work and kinetic and
potential energy changes (Ws, ∆Ek, ∆Ep) are negligible compared to each of the first two
terms in the expression for ∆H, the energy balances implifies to ∆H =O

38
Once again, the reference states for determination of the specific enthalpies in this
equation must be those used to determine the value of ∆Hco . If the heats of combustion
in Table B.1 are used, the reference states would be the fuel, combustion products
(including liquid water), and inert species at 25°C and 1atm. The fuel would be in which
ever state (solid, liquid, or gas) Table B.1 specifies.

39
Example 9.6-2

(nO2)theoretical=1.5 mol

40
 , H2O(l)

From T.B.1

100
0,4147.10 5 0,3191.10 8 1,965.10 12
25CpAir( g ) .dT  28,94.10 (100  25) 
3
(100  25 ) 
2 2
(100  25 ) 
3 3
(100 4  254 )
2 3 4

ni=1
ni=2
ni=1.5
ni=11.28
41
  25 Tad
(2x44.013) H H 2O   Cp H 2O (l ) .dT  H V (25 C )   Cp H 2O ( v ) .dT
o

25 25

42
The furnace walls will therefore never be exposed to a temperature greater than 1256°C as long as the feed and
air properties remain the same.
Example 9.6-2

43
Tamamını Excel’de çözmek için!
D10: Tad değerine yaklaşık bir değer örneğin 100 yaz!

44
45
46
Flamibility and Ignition
Combustion is defined as a rapid, high-temperature oxidation reaction. What happens
in the reactor just described after the reaction rate accelerates dramatically is combustion,
whereas the initial slow oxidation reaction between methane and oxygen to form CO2
And H20 and other reactions between these species, such as the formation reaction of
Formaldehyde are not classified as combustion reactions.

The rapid increase in the rate of an oxidation reaction when the reaction mixture exceeds
a certain temperature is called ignition; the temperature at which this phenomenon occurs
is called the ignition temperature, and the time between the instant when the mixture
reaches the ignition temperature and the moment of ignition is the ignition lag. The
ignition temperature and lag are shown here on a representative plot of the temperature
of a fuel mixture that is being heated.

Ignition lags are typically 0.1-10 s in duration and decrease with increasing
temperature above the auto ignition temperature. 47
ignition temperature depends on a number of things for a given fuel:
fuel-to-air ratio, the total pressure in the reactor, and even the reactor geometry.
For any given fuel, there is a lower limit to this quantity called the autoignition temperature

for stoichiometric fuel-air mixtures at 1 atm autoignition temperature:

H2 400oC
CH4 540oC
C2H6 515oC

The highest attainable temperature in a combustion reaction (adiabatic flame temperature)

depends on the fuel-to-air ratio, this upper temperature limit is a maximum when the fuel and
oxygen are present in stoichiometric proportion.

If the mixture is either rich (fuel in excess) or lean (02 in excess), the adiabatic flame temperature
decreases

There exist two values of the mole percent of fuel in a fuel-air mixture - the lower or lean
flammability limit and the upper or rich flammability limit – that define a range within
which self-sustaining combustion can occur. A fuel-air mixture whose composition falls out-side
these limits is incapable of igniring or exploding, even if exposed to a spark or flame.
The composition range between the two flammability limits is called the explosive range of the
mixture.

48
Forexample:
the stoichiometric percentage of methane in a methane-air mixture is 9.5 mole%

CH4+2O2 → CO2+2H2O air: 3.76 mol N2 + 1 mol O2

For this reaction CH4: 1 mol and O2: 2 mol and N2: 3.76x2 mol
CH4% mol = 1 x100= 9.5%
(1+2+3.76x2)

Experimentally, it is found that the lower flammability limit of CH4-air mixtures at 1atm is
approximately 5% CH4 and the upper flammability limit is approximately 15% CH4. Thus, a
CH4-air mixture containing between 5% CH4 and 15% CH4 must be considered a fire or
explosion hazard, while a mixture containing 3% CH4 may be considered safe, and a mixture
containing 18% CH4 may also be considered safe as long as it is not brought into contact
with additional oxygen.

Flammability limits of a number of hydrocarbon-air mixtures are listed in tables on

pp.26-53 and26-54 of Perry's Chemical Engineers‘ Handbook

49
Example 9.6-3
Propane gas and air are to be mixed and fed to a combustion reactor. The combustion is to be
initiated with a gas torch. Determine the minimum and maximum percentages of propane in the feed
to the reactor and the minimum required temperature of the torch flame.
From Table 26-10 of Perry's Chemical Engineer's Handbook (see footnote I),

Minimum mole %C3H8 for combustion = 2.1%

Maximum mole%C3H8 for combustion = 9.5%
The torch flame temperature must be at least as high as the autoignition temperature of a
propane-air mixture, which from Table 26-10 is 450oC.

If a liquid (or a volatile solid) is exposed to air, the vapor given off could form a combustible mixture
with the air adjacent to it, and a spark or match lit in the vicinity of the liquid could cause the mixture
to ignite or explode. The flash point of a liquid is the temperature at which the liquid gives off enough
vapor to form an ignitable mixture with the air above the liquid surface. The flash point of gasoline,
for example, is roughly -42oC, and that of ethanol is 13oC. So that these liquids constitute fire hazards
at room temperature, while the flash points of fuel oils vary from 38oCto 55oC, making the hazards
associated with these materials considerably less.

50
Suppose a combustible gas-air mixture is contained in an open-ended tube. And a macth or an ignition
source is applied to one end of the tube. The gas mixture at this end is heated and eventually ignites.
At some point, the tube appears as follows:

The flame front moves in the direction of the unburned gases at a velocity called the flame
velocity, which typically has a value of 0.3 to 1 m/s. The exact value of the flame velocity
depends on a number of things, including the type of fuel, fuel-to-air ratio, initial temperature
and pressure of the unburned gases, and the geometry of the combustion chamber. 51
Suppose now that instead of being stationary in the tube, the combustion mixture is fed continuously
into the bottom (as in a Bunsen burner), and the top is ignited. If the velocity with which the gases
leave the tube equals the velocity with which the flame would travel down in a stationary gas, a
stationary flame is achieved at the top. The wall of the tube lowers the flame velocity, so that the
flame burns at the end but does not penetrate into the tube.
If the gas flow rate is increased, the flame size and rate of heat generation both
increase, since a larger quantity of gas is being burned. However, once the flow rate
reaches a critical value, the flame can no longer travel back as fast as the combustion
region is transported away from the burner. The gases in the combustion region
become increasingly diluted with air, until the region finally falls outside the
flammability limits and the fire is literally blown out.
On the other hand, if the gas flow rate to the burner tube is decreased, the gas
velocity in the tube may be come lower than the flame propagation velocity in the
tube. The result is flashback-the flame travels backthrough the tube toward the fuel
source. Flashback is extremely dangerous, and any flow system involving combustible
gases must be designed to guarantee that the flow rate stays above the flame
propagation velocity.
When combustion of a well-mixed fuel-air mixture occurs, flame appears blue.
On the other hand, when the fuel and air are not well mixed, flame appears yellow.

52
Example: calcination

CaCO3 (s) CO2 (g)

900oC
CaO (s)
m=1000 kg/h


CaCO3( s ) 
 CaO( s )  CO2 ( g )

Conversion is 100%. Calculate entalpy change rate as kJ/h

kg 1 kmol kmol
nCaCO 3  1000 x  10
h 100 kg h

Reference: 25oC, 1 atm, Ca(s), C(s), O2(g)

nin Hin nout Hout
CaCO3(s) 10 H1 - -
CaO(s) - - 10 H2
CO2(g) - - 10 H3

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  25
H 1  H 0
f CaCO 3( s )   CpCaCO 3( s ) .dT
25

 900
H 2  H 0
f CaO ( s )   CpCaO ( s ) .dT
25

 900
H 3  H 0
f CO 2 ( g )   CpCO 2( g ) .dT
25


H 1  1206,9 kJ / mol  0

3 4,52.10 10
5
CpCaO ( s )  41,84.10  2,03.10 T  2
kJ / mol.o K
T
1173
2,03.10 5 T 2 4,52.10 10
298CpCaO( s ) .dT  41,84.10 T 
3

2 T

 kJ 3 2,03.10 5 (11732  2982 )  1 1 

H 2  635,6  41,84.10 (1173  298)   4,52.10 10   
mol 2  1173 298 

H 2  585,93 kJ / mol 54
  kJ 3 4,233.10 5 2,887.10 8
H 3  393,5  36,11.10 (900  25)  (900  25 ) 
2 2
(9003  253 )
mol 2 3
7,464.10 12
  (900 4  254 )
H 3  350,56 kJ / mol 4

 
H   ni H i   ni H i
out in

H  [(585,93).10000  (350,6).10000]  [(1206,9).10000]  2703700 kJ / h

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Example 9.5-6:
A 10.0 wt% aqueous solution of H2S04 at 40°C is to be neutralized with a 20.0 wt%
aqueous solution of NaOH at 25°C in a continuous reactor. At what rate in kJ/kg H2S04
solution must heat be removed from the reactor if the product solution emerges at 35°C?

Conversion is not given but we may understand that conversion is 100%. Because
İt is neutralization reaction. NaOH solution is added in stoichiometric amount.

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1.

61
 ratio of H2O
Molar amount of 145 gr
Produced with Na2SO4
Since MW= 142 gr

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3. Calculate extent of reaction:

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Example: H2SO4 Mixing
XH2SO4=10% and Cp≈ 0.9177 cal/g.oC

≈ 3.85 J/g.oC

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Perry's Chemical Engineers' Handbook on p. 2-193 gives the standard heat of
formation of Na2S04 (aq, r = 1100) as - 330.82 kcal/mol Na2S04
= -1384 kJ/mol Na2S04

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 Standard heat of reaction (∆Hr) at 25oC should be calculated;

 o   o   o
For each species;   H f     H f    H s (r )
  solution   solute

H2SO4(l) ∆Hs

NaOH(c) ∆Hs

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