CHAPTER 4

Heat Effects
INTRODUCTION of HEAT TANSFER
4.1 SENSIBLE HEAT EFFECTS
Heat transfer system (x phase transition, x
chemical rxn & x composition) causes the
T of the system only.

T2
Derive: U CV dT (4.1)
T1

T2
H C P dT (4.2)
T1

T2
Q H CP dT (4.3)
T1
 Enthalpy and Heat Capacity

Enthalpy, H : To quantify the heat flow into or out of a

system in a constant pressure process

H = U + PV

The enthalpy of reaction, H : The difference between

the enthalpies of the product and the enthalpies of the
reactant
Enthalpy

Hproducts < Hreactants Hproducts > Hreactants

H < 0 H > 0
 Thermochemical Equation

Is H negative or positive?

System absorbs heat

Endothermic

H > 0

6.01 kJ are absorbed for every 1 mole of ice that melts at 00C and 1 atm.

H2O (s) H2O (l) H = 6.01 kJ

 Thermochemical Equation

Is H negative or positive?

System gives off heat

Exothermic

H < 0

890.4 kJ are released for every 1 mole of methane that is combusted at 250C
and 1 atm.
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) H = -890.4 kJ
 Thermochemical Equation

The stoichiometric coefficients always refer to the number of moles of a

substance

H2O (s) H2O (l) H = 6.01 kJ/mol H = 6.01 kJ

If you reverse a reaction, the sign of H changes

H2O (l) H2O (s) H = -6.01 kJ

If you multiply both sides of the equation by a factor n, then H must

change by the same factor n.

2H2O (s) 2H2O (l) H = 2 mol x 6.01 kJ/mol = 12.0 kJ

 Thermochemical Equation

The physical states of all reactants and products must be specified

in thermochemical equations.
H2O (s) H2O (l) H = 6.01 kJ
H2O (l) H2O (g) H = 44.0 kJ

How much heat is evolved when 266 g of white phosphorus (P4) burn
in air?

P4 (s) + 5O2 (g) P4O10 (s) Hreaction = -3013 kJ

1 mol P4 3013 kJ
266 g P4 x x = 6470 kJ
123.9 g P4 1 mol P4
 Heat Capacity

Heat capacity, C : the amount of heat requires to raise the temperature

of a given quantity of substance by one degree Celcius
Specific heat, s : The amount of heat required to raise the temperature
of one gram of the substance by one degree Celcius

Specific heat, s = J/goC

C=ms Heat capacity, C = J/oC

Where m is mass in gram

Example: The specific heat of water is 4.184 J/g.oC
and heat capacity of 60 g of water is
(60 g) (4.184 J/goC) = 251 J/oC
 Heat Capacity

The relation between amount of heat change (q) with specific heat (s),
amount of substance (m) and temperature change (T) is :

q=msT q=CT Where T = Tfinal - Tinitial

Example: A 466 g sample of water is heated from 8.5oC to

Note
74.6oC. Calculate the amount of heat absorbed by the q is positive for
water endothermic
process
Solution: Q is negative for
q = ms T exothermic process

= (466 g) (4.184 J/g.oC) (74.60-8.5)oC = 129 kJ

 4.2 LATENT HEAT OF PURE
SUBSTANCE

Drawing of an experiment to measure the latent heat of vaporization as steam

condenses to water.
PHASE RULE : 2-phase system consisting of a single species is univariant, and
its intensive state is determined by the specification of just 1 intensive
property. Thus the latent heat accompanying a phase is a function
of T only, and is related to other system properties by an exact
thermodynamics eq.:

(Clapeyron Equation)
dP sat
H T V (4.11)
dT
 Applying Eq. 4.11 to the vaporization of pure liquid, dPsat/dt is the slope
of vapor pressure vs T curve at the T of interest

V = difference between molar volumes of saturated vapor and

saturated liquid

H = latent heat of vaporization (calculated from vapor pressure &

volumetric data / measured calorimetrically)
 STANDARD HEAT OF
FORMATION, HOf298
Standard enthalpy of formation (H0) is the heat change that
results when one mole of a compound is formed from its elements
at a pressure of 1 atm.
A formation reaction = Rxn which form a single compound form its
constituent element
f = heat of formation

The standard enthalpy of formation of any element in its most

stable form is zero.

H0 f(O2) = 0 H0 f(C, graphite) = 0

H0 f(O3) = 142 kJ/mol H0 f(C, diamond) = 1.90 kJ/mol
 STANDARD HEAT OF
REACTION, HORXN
The standard enthalpy of reaction (H0rxn) is the enthalpy of a reaction
carried out at 1 atm.
aA + bB cC + dD

H0rxn = [cH0f (C) + dH0f (D) ] - [aH0f (A) + bH0f (B) ]

H0rxn = S n H0f (products) - SmH0f (reactants)

Hesss Law: When reactants are converted to products, the

change in enthalpy is the same whether the reaction takes place in
one step or in a series of steps.

(Enthalpy is a state function. It doesnt matter how you get there, only where
you start and end.)
 EXAMPLE
Benzene (C6H6) burns in air to produce carbon dioxide and liquid water. How
much heat is released per mole of benzene combusted? The standard enthalpy of
formation of benzene is 49.04 kJ/mol.

2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

H0rxn = S H0 f(products) - S H0 f(reactants)

H0rxn = [12H0f (CO2) +6H0f (H2O) ] - [ 2H0f (C6H6) ]

H0rxn = [ 12 -393.5 + 6 -285.8 ] [ 2 49.04 ] = -6535 kJ

-6535 kJ
= - 3267 kJ/mol C6H6
2 mol
Calculate the standard enthalpy of formation of CS2 (l) given that:
C(graphite) + O2 (g) CO2 (g) Hrxn
0 = -393.5 kJ

S(rhombic) + O2 (g) SO2 (g) Hrxn

0 = -296.1 kJ

CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) Hrxn

0 = -1072 kJ

1. Write the enthalpy of formation reaction for CS2

C(graphite) + 2S(rhombic) CS2 (l)

2. Add the given rxns so that the result is the desired rxn.
C(graphite) + O2 (g) CO2 (g) Hrxn
0 = -393.5 kJ

2S(rhombic) + 2O2 (g) 2SO2 (g) Hrxn

0 = -296.1x2 kJ

CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) Hrxn

0 = +1072 kJ

C(graphite) + 2S(rhombic) CS2 (l)

H0rxn= -393.5 + (2x-296.1) + 1072 = 86.3 kJ
 Supplementary Problems
1. Calculate the standard enthalpy of formation of C2H2 (g) from its element
2C(graphite) + H2(g) C2H2 (g)
C(graphite) + O2 (g) CO2 (g) Hrxn
0 = -393.5 kJ

rxn
2C2H2(g) + 5O2 (g) 4CO2 (g) + 2H2O (l) H0rxn= -2598.8kJ

2. From the following data,

C (graphite) + O2(g) CO2 (g) Horxn = -393.5kJ
H2 (g) + O2 (g) H2O(l) Horxn = -285.8kJ
2C2H6 (g) + 7O2 (g) 4CO2 (g) + 6H2O (l) Horxn = -3119.6kJ
Calculate the enthalpy change for reaction
2C (graphite) + 3H2 (g) C2H6 (g)
 Supplementary Problems
3. From the following heats of combustion,
CH3OH (l) + 3/2O2(g) CO2 (g) + 2H2O (l) Horxn = -726.4kJ
C (graphite) + O2 (g) CO2(g) Horxn = -393.5kJ
H2 (g) + 1/2O2 (g) H2O (l) Horxn = -285.8kJ
Calculate the enthalpy change for reaction
C (graphite) + 2H2 (g) + O2 (g) CH3OH (g)

4. From the following data,

C (graphite) + O2(g) CO2 (g) Horxn = -393.5kJ
H2 (g) + O2 (g) H2O(l) Horxn = -285.8kJ
2C2H6 (g) + 7O2 (g) 4CO2 (g) + 6H2O (l) Horxn = -3119.6kJ
Calculate the enthalpy change for reaction
2C (graphite) + 3H2 (g) C2H6 (g)
TEMPERATURE DEPENDENCE
OF Ho
General chemical reaction;
lv1lA1 + lv2lA2+lv3lA3 + lv4lA4+
lvil=stoiciometric coefficient
Ai = Chemical formula
Species (left) = Reactant
Species (Right)= Product
(+) for PRODUCT & (-) for REACTANT
H o i H io (4.14)
i
 Hoi = Hof if standard-state enthalpies of all elements are arbitrarily
=0

Eq. 4.14 becomes:

H o i H ofi (4.15)
i

CPo i CPoi (4.16)

i

dH o CPo dT (4.17)
THANK YOU