Heat Effects exactly true for the ideal-gas state and

approximately true for real gases at low

Topics: pressure and high temperature.
I. Sensible Heat Effects
II. Latent Heats of Pure substances
III. Standard Heat of Reaction
IV. Standard Heat of Formation
V. Standard Heat of Combustion Example 1
VI. Temperature Dependence of ΔH° Hot oil at To1 is supplied to a heater to heat air
VII. Heat Effects of Industrial Reactions entering at Ta1. The oil exits at To2 and the air
heater is totally insulated. Do the energy balance in
ordered to determine the outlet air temperature T
Heat Effects - refer to physical and chemical a2.

phenomena that are associated with heat transfer

to or from a system or that result in temperature
changes within a system, or both.

I. Sensible Heat Effects Energy Balance: dH + du2/2 +gdz = Q + WS

 Temperature of the system is caused to dH + du2/2 +gdz = Q + WS
change dH = 0
 No reaction, No phase change and No (Ho2 + Ha2) – (Ho1 + Ha1) = 0
composition change Assume air is an ideal gas:
T T

∫ C lp ,0 +∫ C igp ,a dT =0
¿ ¿
Assume constant Cp
C lp ,0 ( T ❑O 2 −T O 1 ) +C igp , a ¿) = 0
ig l
C p , a T A 1 −C p , o (T o 2−T o 1)
T A 2= ig
C p, a
 For a homogeneous substance of constant
composition in a system, two intensive ღ Temperature Dependence of the Heat
properties establishes its state Capacity
 Thus, for molar or specific internal energy, Cp 2 −2
= A+ BT +C T + D T
U = U(T,V) R
 A, B, C, amd D are constants for heat
capacity and values for ideal as, solid and
liquid
 Unit is governed by R
a.) Constant Volume (closed system)
b.) U is independent of Volume, as for
ideal-gas state and incompressible fluid



ღ Evaluation of Sensible Heat Integral (Mean

Heat Capacity)
 Similarly for Enthalpy, H = H(T,P)


a.) For any Constant P process
b.) When the enthalpy is independent of
pressure, regardless of process. This is
 {(
Q= A +
B
2
C
( T −T 0 )+ ( T 2 +T 20+TT ❑0 ) +
3
D
T T0 )}
R ( T −T

{(
9.1 −2.164
3 6
mean heat capacity 10 10
Q= 1.702+ ( 873.15 K −533.15 K ) + ( (873.1
2 3
Q = 19777.52218 J

(Using Perry’s Formula)

C1 = 0.33298 x 10-5
C2 = 0.79933 x 10-5
C3 = 2.08690 x 10-3
C4 = 0.41602 x 105
9th Ed: 2-147, Constants C5 = 991.96

[ ( )] [ ( )]
Example 4.2 C3
2
C5
2

Calculate the heat required to raise the 0 T T

temperature of 1 mol of methane from 260 to C ❑p =C 1+C 2 +C 4
C3 C5
600°C in a steady flow process at a pressure sinh cosh
T T
sufficiently low that the ideal-gas state is a suitable

[ ( )] [
2
approximation for methane. C3 C5
T2 873.15
*temp change + steady flow = perry’s mean heat T T
Q=∫ C p dT = ∫ C 1+C 2
0
+C 4
capacity T1 533.15
sinh
C3
T
cosh
C
(
T

[
Given:
Methane 2.08690 x 103
873.15
T
T1 = 260C = 533.15K Q= ∫ 0.33298 x 10 5+ 0.79933 x 105
T2 = 600C = 873.15K
N = 1 mol CH4
533.15
sinh ( 2.08690T x 10
Q = 19775553.32 J/kmol /1000
Required: Q
Q = 19775.55332 J/mol

Solution: (Using Van Ness Constants)

Q=∆ H=( C p ) H ( T −T 0 ) Example 4.3
(C p)H B C 2 2 D What is the final temperature when heat in the
= A+ ( T −T 0 ) + ( T +T 0 +TT ❑0 )+
R 2 3 T T0 amount of 400 × 106 J is added to 11 × 103 mol of
ammonia initially at 530 K in a steady-flow process
( B C D
( C p ) H = A+ 2 ( T −T 0 ) + 3 ( T 2+ T 20 +TT ❑0) + T T
0
) R at 1 bar?

{(
Q= A +
B
2
C
( T −T 0 )+ ( T 2 +T 20+TT ❑0 ) +
3
D
T T0 )} Given:
R ( T −T 0)
Q = 400x106 J = dH
n = 11x103 mol NH3
From Van Ness Appendix C: T0 = 530 K
9.801 = 103 B -2.164 = 106 C Required: Final T
9.801 −2.164 Solution: (Van Ness Constants)
B= C=
103 10 6
∆H
T= +T0
A = 1.702 D=0 (C p)H
∆H
T= + T0
( )
R = 8.314 J/mol K B C 2 2 D
A+ ( T −T 0 ) + ( T +T 0 +TT ❑0 ) + R
2 3 T T0
 Q Q/n = 35299927.11
n
T= + T0
( )
B C D If T = 1250 K
A+ ( T −T 0 ) + ( T 2+T 20 +TT ❑0 ) + R Q/n = 38381838.48
2 3 T T0
400 x 106 J
T = 1216.634985 K
11 x 10 3 mol T = 1217.257298 K
T= +T
( )
0
B C D J
A+ ( T −T 0 ) + ( T 2+T 20 +TT ❑0 ) + 8.314
2 3 T T0 mol K Heat of Pure Substances
II. Latent
Latent Heat
– pure substance undergoing phase change
From Van Ness Appendix C: without a change in temperature
3.020 – Initial condition is saturated liquid at T1 (or
B= C= 0
103 T1 sat) and P1 (or P1 sat)
−0.186 – Final condition is saturated vapor at T1 and
A = 3.578 D=
10 5 P1 (last drop of liquid is to disappear)
– Application of degrees of freedom results
6
400 x 10 J to: F= 1-2+2 = 1
– Thus, once we specified one
11 x 103 mol
T= thermodynamic properties,+(530 other K)

( )
3.020 −0.186
properties will depend on this.
103 0 10 −5
J
3.578+ (T −530 K ) + ( T 2 + ( 530 K )2 +T (530 K )) + 8.314
2 3 T (530 K )Equationmol
 Clapeyron K
to estimate dHvap

T = 1233.96 K****

(Using Perry’s Constants)

C1 = 0.33427 x 105  Steam Table (psat, Hvsat, Hlsat)
C2 = 0.48980 x 105
C3 = 2.03600 x 103
C4 = 0.22560 x 105  Trouton’s Rule (rough estimate of latent
C5 = 882 heats of vaporization for pure liquids at

[ ( )]
their normal boiling points)
2
882

[ ]
6 T 3 2
400 x 10 mol 2.036 x 10 T
=∫ 0.33427 x 10 +0.48980 x 10
5 5 5
x 1000 +0.22560 x 10
( )
3
11 x 10 mol 1 kmol 530 2.036 x 10
3
882
sinh cosh
T boiling point)
 Riedel (normal T

[ ( )]
2
882

[ ]
T 3 2
2.036 x 10 T
36363636.36=∫ 0.33427 x 10 + 0.48980 x 10
5 5 5
+0.22560 x 10
( )
882
3
530 2.036
 xWatson
10 cosh
(any temperature)
sinh
T T

TRIAL AND ERROR:

If T=1060K
Q/n = 26956910.23 J/kmol
Example 4.4
Given that the latent heat of vaporization of water
If T = 1500 K
at 100°C is 2257 J ⋅ g−1, estimate the latent heat at
Q/n = 54483158.51
300°C.

If T = 1200 K
Given:
T1 = 100°C - Energy balance:
T2 = 300°C
dH1 = 2257 J ⋅ g−1
Required: dH2
Solution:
Tc = 647. 096 K
100+273.15
T r 1= = 0.5767
647.096
300+273.15
T r 2= = 0.8857
647.096

( )
∆ H 2 1−T r 2 0.38
=
∆ H 1 1−T r 1

( )
∆ H2 1−0.8857
0.38
 All conditions for a standard state are fixed
=
J 1−0.5767 except temperature, which is always the
2257 temperature of the system. Standard-state
g
J properties are therefore functions of
∆ H 2 =1372.343358 temperature only.
g
III. Standard Heat of Reaction  When a heat of reaction is given for a
Heat of Reaction particular reaction, it applies for the
 enthalpy change of reaction, dH stoichiometric coefficients as written. If
 change in the enthalpy of a chemical each stoichiometric coefficient is doubled,
reaction that occurs at a constant pressure. the heat of reaction is doubled.
 Heat is released or absorbed during the
process

 EXOTHERMIC: dH is –
 ENDOTHERMIC: dH is +

Energy balance for steady-state open system: The symbol ∆H0298 indicates that the heat of reaction
is the standard value for a temperature of 298.15 K
(25°C) and for the reaction as written.

IV. Standard Heat of Formation, dHf,i0

Formation Reaction - reaction that forms a single
compound from its constituent elements

Vi -> stoichiometric coefficient of reactants and  For formation of 1 mol of compound Ai

products form its element (E)

ღ Standard Heat of Reaction, dHT0

- enthalpy change from a stoichiometric
reaction where the reactants entering
 Here Hi0 is calculated with reference to its
at standard state (for a given T, and P=1
elements’ enthalpy (He0) to be zero at
bar, specified phase (g,l,s)) and the
standard state (given the reference T of
products are also at specified phases
T=298.15K )
and the same standard state
 dH2980 = -27.3438 x 103 cal x 4.184 J/cal
dH2980 = -114 406.46 J

V. Standard Heat of Combustion

Standard Heat of Combustion
- a reaction of an element or compound
with oxygen to form specified
 Example: combustion products
- A reaction between fuel (organic
compounds consisting only of C, Hand
O) and oxygen to produce water and
 Perry’s Heat of Formation: carbon dioxide
- The value for liquid water product is
Example (Calculation of std heat of rxn using std called the higher heat of combustion,
heat of formation) while that with water vapor as product
is the lower heat of combustion.
CO2 (g) + H2 (g) -> CO (g) + H2O (g) - Reactants has higher chemical energy
than the products, therefore the heat
of combustion is negative.
- Data are always based on 1 mol of the
substance burned
- Calculation:

Notes:
 H2O does not actually exist as gas at 25oC
and 1 bar.
VI. Temperature Dependence of dH°
 This is hypothetical state of H2O as an ideal
 Most reactions in the industry occur at
gas at 25oC and 1 bar is used for
temperature other than standard state.
convenience in calculation.
 For example, reactants enter a reactor at
 Notice also the standard heat of formation
200°C and the products exit 200°C, so std
of H2O is tabulated for liquid as well as gas
heat of reaction is ∆H473.150
at the standard state (1bar, 25oC).
 Since H is state function, we can use
hypothetical path to determine ∆H 473.15
Example 4.5
Calculate the standard heat of reaction at 25°C for
the following reaction:

4HCl(g) + O2 (g) -> 2 H2O (g) + 2 Cl2 (g)

dHf298, HCl0 = -22.063 kcal/mol

dHf298, O20 = 0
dHf298, H2O0 = -57.7979 kcal/mol
dHf298, Cl20 = 0

0
∆ H 298 =Σ v ❑i H ❑ products −Σ v i H products o Path representing the procedure
dH 298
0
= [(2)(-57.7979)+(2)(0)] –[(4)(-22.063)+(1)(0)] for calculating a standard heat of
dH 298
0
= -27.3438 kcal reaction at temperature T from the
value at reference temperature T0.
  For example, reactants enter a reactor at CO(g) + 2H2 (g) → CH3OH(g)
200°C and the products exit 200°C, so std
heat of reaction is ∆H473.150 T = 800C = 1073.15K

(Using Van Ness Constants)

 ∆H473.150 = ∆Hreactants + ∆H2980 + ∆Hproducts

 ∆H473.150 = Sensible Heat + Std Heat of Rxn at
298 + Sensible Heat

0 0
∆ H 473.15=Σreactants 473→ 298 n i C p dT +d H 298 + Σ products 298→ 0473 ni C p 0dT
∆ H T =∆ H 298 + ( ∆ C p ) H (T −298)
0


0 0
∆ H 473.15=Σreactants 298→ 473 n i C p dT +d H 298 + Σ products 298→ 473 ni C p dT

0 0
(
∆ H 473.15=d H 298 + Σ products 298→ 473 n i C p d T −Σ reactants298 → 473 ni C p dT
∆B ∆C
( ∆ C0p ) H =R ∆ A+ 2 ( T +T 0 ) + 3 (T 2+T 20 +T T 0 )+ T T
∆D
0

∆ A=( 1 ) (2.211 ) −( 1 )( 3.376 )−( 2 ) (3.249 )=−7.663

 ni = |vi|
∆ B=( 1 ) ( 12.216 x 10 )−( 1 ) ( 0.557 x 10 )−( 2 ) ( 0.422 x 10
−3 −3

−6
0 0 ∆ C=0.422
∆ H 473.15=d H 298 + Σ products298→ 473 n i C p dT −Σ reactants298→ x 10
473 ni C p dT

∆ D=−13500
0 0 0 0
∆ H 473.15=d H 298 + Σ v i C p dT =d H 298 +d C p dT
∆ H T =∆ H 298 + ( ∆ C p ) H (T −298)
0 0 0

∆ H 298 =[ ( 1 ) (−200660 ) ] −[(1)(−110525)]

0

Where, ( ∆ C p ) H ≡ Mean Heat Capacity for

0 0
 ∆ H 298 =−90135 J
Reaction
0
and ∆ H 1073.15 =−90135 J +−17.3303 ( 1073.15−298 )

(∆B ∆C ∆D
)
0
( ∆ C0p )H =R ∆ A+ 2 ( T +T 0 ) + 3 (T 2+T 20 +T∆TH0 )1073.15
+ =−103 568.58 J
T T0
and dM = EviMi and M is A, B, C, D constants (Using Perry’s Constants)
for heat capacity

J
C 0p ,CO dT =24 130.8201
mol−K
J
C 0p , H 2 dT =2 2 891.3053
mol−K
0 J
C p ,C H 3 O H dT =55158.0853
mol−K

Example 4.6 T
Calculate the standard heat of the following ∆ H 01073.15 =∆ H 0298 + Σ v i ∫ C0p , i dT
methanol-synthesis reaction at 800°C: T0
0 0
∆H 1073.15 =∆ H 298 +¿
∆ H 1073.15 =−90135 J + ( ¿ ¿−[ ( 1 )( 24 130.8201) +(2)( 22891.3053)])
0

0
∆ H 1073.15 =−104 890.35 J

VII. Heat Effects of Industrial Reactions

 Most reaction in industry rarely occur at
25oC, 1bar and also not at stoichiometric
proportion.
 Reactants always contains excess
component.
 The reaction does not always go to
completion (not 100% conversion)
 Outlet Temperature is not the same as the
inlet
 Presence of inert materials
 More than one reaction may take place
simultaneously

Example 4.7
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.
CH4 + 2O2 + 2(79/21)N2 -> CO2 + 2H2O + 2(79/21)N2
With 20% excess air,
CH4 + 1.2(2O2) + 1.2(2(79/21)N2) -> CO2 + H2O
0.2(2O2) + 1.2(2(79/21)N2)

Basis: 1 mol CH4

Energy Balance:
Q+W s=∆ H + ∆ KE+ ∆ P E
∆ H =0

At max temp, Q=0