CHAPTER 3

HEAT EFFECT
 Outline

• Sensible Heat Effects

• Latent Heats of Pure Substances
• Standard Heat of Reaction
• Standard Heat of Formation
• Standard Heat of Combustion
 Learning Outcome

At the end of the lesson, students should be able

to:

•Evaluate heat effects that accompany by

physical and chemical operations
Sensible Heat Effect
• Heat transfer to a system in which there are no phase
transitions, no chemical reactions, and no changes in
composition causes temperature change of the system

• Develop the relations between the heat transferred and the

resulting temperature change

• For a mechanically reversible, constant-volume process:

T2
Q  U   CV dT
T1

• For a mechanically reversible, constant-pressure process:

T2
Q  H   C P dT
T1
 Heat Capacity for Gas Mixtures

• In an ideal-gas mixture, each gas exists

independent of the others

• Ideal-gas heat capacity of a mixture is therefore

the mole-fraction-weighted sum of heat
capacities of individual gases

• For gases A, B and C, the molar heat capacity of

a mixture in ideal-gas state is:

C ig
Pmixture  y AC ig
PA  yBC ig
PB  yC C ig
PC
Latent Heat of Pure Substance
• When a pure substance is liquefied from solid
state or vaporized from liquid at constant P, no
change in T occurs.

• However, the process requires heat transfer to the

substance.

• These heat effects are called the latent heat of

fusion and the latent heat of vaporization.
• Latent heat accompanying a phase change is a
function of temperature only, and is related to
other properties by an equation:

dP sat
H  TV
dT

where for a pure substance at T:

ΔH - latent heat
ΔV - volume change due to phase change
Psat - saturation pressure
• Rough estimates of latent heats of vaporization for
pure liquids at normal boiling points are given by
Trouton’s rule:

H n
 10
RTn
• Another equation proposed by Riedel is:

H n 1.092 ln Pc  1.013

RTn 0.930  Trn
where: Tn - Temperature of normal boiling
point
Pc - Critical pressure in bars
Trn - Reduced temperature at Tn
• A method to estimate the latent heat of
vaporization of a pure substance at any
temperature based on a known value at a single
temperature is proposed by Watson:

0.38
H 2  1  Tr 2 
  
H 1  1  Tr1 
Standard Heat of Reaction
• For the reaction
aA  bB  mM  nN

Standard heat of reaction is defined as the

enthalpy change when a moles of A and b moles
of B in their standard states at T react to form m
moles of M and n moles of N in their standard
states at the same T.

• Heat associated with a specific chemical reaction

depends on the temperatures of both reactants
and products.
• A standard basis for reaction heat effects results
when products and reactants are all at the same
temperature

• A standard state is a particular state of a species at

temperature T and at specified conditions of
pressure, composition and physical conditions, e.g.
gas, liquid or solid

• Standard states for different substances:

(i) Gases: Pure substance in ideal-gas state at 1 bar
(ii) Liquids & solids: Real pure liquid or solid at 1 bar
• Property values in the standard state are denoted
by degree symbol.

• Example: ΔH°298 = standard heat of reaction at

298.15 K (25 °C).

• When heat of reaction is given for a particular

reaction, it applies for the stoichiometric
coefficients as written
1 3 H  298  46,110 J
N 2  H 2  NH 3
2 2
N 2  3H 2  2 NH 3 H  298  92,220 J
Standard Heat of Formation
• A formation reaction is defined as a reaction which
forms a single compound from its constituent
elements. Eg:
1
C  O2  2 H 2  CH 3OH
2
• Heat of formation is based on 1 mole of the
compound formed.
• Standard heat of formation of a compound at
298.15 K (25 °C) is represented by ΔH°f 298.
• The standard heat of any reaction can be calculated
if the Standard Heat of Formation of the compounds
taking part in the reaction are known.
• Formation equations and standard heats of
formation can always be combined to give any
desired equation and its accompanying standard
heat of reaction.

• Formation equation can be written in reverse so

that their sum yields the desired reaction, and
thus it is in opposite sign to its standard heat of
formation.
• For reaction

CO2 ( g )  H 2 ( g )  CO( g )  H 2O( g )

From the standard heat of formation:

CO2(g): C ( s)  O2 ( g )  CO2 ( g ) H  f 298  393,509 J

H2(g) : Because H2 is an element H  f 298  0 J

1
CO(g): C ( s )  2 O2 ( g )  CO( g ) H  f 298  110,525 J

1 H  f 298  241,818 J
H2O(g): H 2 ( g )  O2 ( g )  H 2 O ( g )
2
• Standard heat of reaction can be obtained from
the standard heat of formation:

CO2 ( g )  C ( s)  O2 ( g ) H  298  393,509 J

1 H 298  110,525 J
C ( s )  O2 ( g )  CO( g )
2
1 H  298  241,818 J
H 2 ( g )  O2 ( g )  H 2 O ( g )
2

CO2 ( g )  H 2 ( g )  CO( g )  H 2 O( g ) H  298  41,166 J

Standard Heat of Combustion
• Combustion reaction is a reaction between an
element or compound with oxygen to form
specified combustion products.

• Many standard heats of formation come from

standard heats of combustion.

• For organic compounds made up of C, H and

O only, the products are CO2 and H2O.

• Data are always based on 1 mole of the

substance burned.
• For the formation of n-butane:

4C ( s )  5 H 2 ( g )  C 4 H 10 ( g )
• By combining the combustion reactions:

4C ( s)  4O2 ( g )  4CO2 ( g ) H  298  (4)(393,509)

5H 2 ( g )  2 12 O2 ( g )  5H 2 O (l ) H  298  (5)(285,830)

4CO2 ( g )  5H 2 O(l )  C 4 H 10 ( g )  6 12 O2 ( g ) H  298  2,877,396

4C ( s )  5 H 2 ( g )  C 4 H 10 ( g ) H  298  125,790 J