HEAT EFFECTS

Notes Set 3
HEAT EFFECTS
Heat Effects refer to physical and chemical phenomena that are associated with
heat transfer to or from a system or that result in temperatures within the system.
Examples of heat effects.
• Sensible heat effects, characterized by temperature changes
• Heat capacities
• Heat of phase transition known as latent heats
• Chemical reactions characterized by heat of reaction.
• Heat of formation, heat of combustion.
Others include the metabolism of human body, chemical manufacturing
processes such as that of ethylene glycol.
SENSIBLE HEAT EFFECTS
• This the heat transfer to or from the system where there is no change of
phase, no chemical reaction and no change in composition
• Is the change in temperature of a substance without a change in it’s phase
• Refer to changes in temperature of the system produced by heat transfer
to or from a system in which there are no phase transitions, chemical
processes or compositional changes.
Explanation
When heat is added or removed from a substance, it results into a
temperature change that can be sensed or measured by a thermometer
without change in physical state. It’s called so, because it is a form of heat
energy that human senses can detect through touch.
A graph illustrating sensible heat effects and
latent heats
Sensible Heat Equation
• Q=mcdt
• Q-Sensible heat, m-mass of substance, c-specific heat capacity of the
substance.
• C- is either at constant volume or constant pressure
• At constant pressure , Q=mdt where -molar heat capacity at constant
pressure
• At constant pressure, Q=mdt where -molar specific heat capacity at
constant volume.
APPLICATIONS OF SENSIBLE
HEAT EFFECTS
• Heat exchangers in industries like in chemical processing ,power
generation and HVAC. These transfer sensible heat between fluids to
regulate temperature in processes like heating, cooling.
• Measurement of temperature in thermometers where the sensible
heat affects the variation of the thermometric properties which
indicates a temperature change.
• Indoor environment for thermal comfort through air conditioners.
• Used in fire alarms specifically heat detectors that respond to a rise in
temperature cause by sensible heat during a fire.
Heat effects accompanying
change of phase of pure
substances
• A phase is a distinct homogeneous part of system that is physically
and chemically uniform throughout.
• The heat effect that causes change in phase of a substance is called
latent heat.
• Definition; latent heat refers to amount of heat absorbed or released
during change in phase without changes in temperature.
Examples of phase changes
• Melting- the change from solid to liquid at constant temperature.
• Freezing –change from liquid to solid
• Vaporization-change from liquid to gas
• Condensation-change from gas to liquid.
• Sublimation –change from solid to gas.
• Deposition –change from gas to solid
• NOTE; all the phase changes occur at constant temperature because
all the heat absorbed or released is entirely used to deal with the
intermolecular forces of attraction between the molecules until its
complete there will be no rise or fall in temperature.
LATENT HEAT OF FUSION
This is the amount of energy required to change any given mass of a
substance from solid to liquid or vice versa at a constant temperature.
Specific latent heat of fusion- Is the amount of energy required to
change a 1kg mass of a substance from solid to liquid or vice versa.
Q=m where -the specific latent heat of fusion.
LATENT HEAT OF VAPORIZATION
This the amount of energy required to change any given of a substance
from liquid to gas or vice versa.
Specific latent heat of vaporization is the amount of energy required
to change a 1kg mass of a substance from liquid to gas or vice versa at
constant temperature. Q=m.where specific latent heat of vaporization.
LATENT HEAT OF SUBLIMATION
This is amount of heat energy required to change any mass of a
substance from solid to gas or vice versa at constant temperature.
Examples of substances that sublime.
• Dry ice/ solid carbon dioxide at -78.5c
• Iodine
• Ammonium chloride.
Variation in molar volume with pressure at
various constant temperatures of a pure fluid
e.g. water
Description
• Assume the system is initially at a state, a.
• Since the fluid is almost incompressible, the reduction of pressure at a
constant tempersture,T1 causes a negligible change in volume until
point b.
• At point b, vaporization begins which results into a rapid increase in
volume from b-d where the two phases liquid and water are in
equilibrium.
• The pressure at which the liquid and vapour phases co-exist in
equilibrium is called the saturation pressure and the temperature
corresponding to this pressure is called the saturation temperature.
• The relative amounts of vapour and liquid phases in equilibrium
change with continued vaporization, and at point d, the entire liquid
has been vaporized.
• Further reduction in pressure increases the volume of the system
along d-e.
• When a higher constant temperature T2 is applied, the horizontal
section between saturated vapour and saturated liquid is much
shorter.
• When the temperature of the system increased to critical
temperature, Tc the saturated liquid and vapour phases become
indistinguishable.
• The liquid state changes to the vapour state without any discontinuity
at point C.
• The locus of the saturated phases is represented by the dome-shaped
curve b-c-d.
• If the temperature is less than the substance to the right of the
saturated line is vapour and if the temperature is more than the
critical temperature, the substance to the right is a gas.
• A vapour can be cooled at a constant pressure or by compressing it at
a constant temperature while a gas can only be condensed by
reduction in temperature at a constant pressure.
HEAT OF REACTION
• This refers to the amount of heat exchanged between a system and its
surroundings when a chemical reaction occurs.
• The amount of heat required to cause a substance to change
temperature follows the equation Q=MC(t)
• The amount of heat released or absorbed during a phase change
follows the equation(s) Q=h * (no. of moles of reactant) if h is in KJ
per mole.
• h is latent heat
Questions
• How much heat is required to melt 60.1g of ice to liquid water?(h of
fusion of water is 6.02KJ/mol)
• How much heat must be absorbed to turn 10.0g of ice at -15c in to
liquid water at 25c?(specific heat of ice=2.06J/gc ,specific heat of
water= 4.18J/gc and h of fusion =6.02KJ/mol)
HEAT OF FORMATION
DEFINITON
• Heat of formation is defined as the change in enthalpy accompanying
the formation of one mole of a substance from its constituent
elements.
What is standard heat of formation
• The standard heat of formation of a compound is the change of
enthalpy that accompanies the formation of 1 mole of a substance in
its standard state from its constituent elements in their standard states
[the most stable form of the element is one atmosphere of pressure
and specified temperature usually 298K or 25 degrees Celsius]
• The standard enthalpy of formation of carbon dioxide would be the
enthalpy of the following reaction under the conditions above;
The standard enthalpy of the formation is measured in units of energy per amount
of substance most defined as kilojoules per mole
NOTE
Forms one mole of a single product
Reactants are elements in their standard states
• All elements are in their standard states [oxygen gas ,carbon ,hydrogen gas etc.
have a standard enthalpy of formation of zero as there is no change involved in
their formation]
The standard enthalpy change of formation is used in thermochemistry to find the
standard enthalpy change of reaction. This is done by subtracting the sum of the
standard enthalpies of formation of the reactants from the sum of the standard
enthalpies of formation of the products, as shown in the equation below.

Δ = ΣΔH (Products) - ΣΔH (Reactants)

1) calculate the heat of formation of methane gas from the following
heat of combustion data.
(a) CH4 (g) +2O2 (g) CO2 (g) +2H2O(l) ΔHƟf298=-890.94KJ
(b) C(s) + O2 (g) CO2 (g) ΔHƟf298=-393.78KJ
(c) H2 (g) +½O2 (g) H2O(l) ΔHƟf298=-286.03KJ
2) Using the following data to calculate the
enthalpy of the reaction.
 HESSS LAW
Hess's Law states that the net heat evolved in a chemical process is the
same whether the reaction takes place in a single step or in a series of
steps.
A
Example
Use Hess's Law calculate the heat of formation from the combustion
data given below.
•3
Thermodynamic data
•2 113 KJ
•2 163 KJ
• 181 KJ
HEAT OF REACTION
• Heat of reaction can also be referred to as Enthalpy of reaction.
• This is the difference between the heat content of products and that of the
reactants.
• The enthalpy change can either be a (+)value meaning its an endothermic
reaction or a(-) value implying that it’s an exothermic reaction.
• When we talk about the enthalpy change ,we must state the temperature ,
pressure , concentration and the physical state of the substance
(gas ,solid ,liquid).
Standard state of a substance is the state in which a pure substance exists at
a specified physical state at a pressure of 1 atmosphere and temperature of
298K.
Standard enthalpy of reaction( 298) is the heat absorbed or evolved when
molar quantities of reactant in their normal physical state react to form
products at pressure of 1atmosphere and temperature of 298K.
The standard heat of reaction can be calculated using the following formulae;

 rxn =(heat of formation of the products )-(heat of formation of the
reactants)

OR  =(heat of combustion of the products )-(heat of combustion
rxn
of the reactants)
The heat absorbed or evolved is a reaction depends on the stoichiometric
numbers of the reacting species , for example

1) C(S) + 1/2 O2(g)  CO(g) ;  298
= -110.6 kj
2) 2 C(S) + O2(g)  2C0(g) ; 298 =221.2 kj

Question
1 ) Calculate the standard enthalpy of reaction;

C2H2 (g) +H2O(l)  C2H6O(l)

The standard heat of formation of ethene is (+52),water is (-286),ethanol is (-278) kJmol-
HEAT OF COMBUSTION

Standard heat of formation(  ) is the heat evolved when one mole
f
of a substance is completely burnt in oxygen at a pressure of 1
atmosphere and temperature of 298K.
The enthalpy o combustion is always a negative value implying that its
an exothermic process
The element /compound should exist in its normal physical state.
The enthalpy of combustion of hydrogen to form liquid water is
known as the Higher heat of combustion while that when water vapour
is formed is called the Lower heat of combustion
QUESTIONS
1) Calculate the enthalpy of combustion of benzene ,given that the enthalpy of combustion of
carbon is -393kjmol-,enthalpy of formation of benzene is +82.84kjmol- and the enthalpy of
formation of water is -285kjmol-
2) Calculate the standard heat of reaction of the following reaction at 298K:
CO2(g) + 8O2(g)  5CO2(g) + 5H2O(g)
The standard heats of formation are as follows :
CO2(g) =-393.509KJ ,H2O(g) =-241.818KJ, C5H12(g) =-146.76KJ
The latent heat of vaporization of water at 298K is 43.967kJ/mol.
3): Calculate the enthalpy of combustion of acetaldehyde C2H2 given the enthalpies of formation
of the following reaction.
C2 H2 (g) + 5/2O2 (g) 2CO2 (g) + H2 0(l)
ΔHƟ C2H2 (g) =-226.73KJmol-1
ΔHƟ CO2 (g) =-393.5KJmol-1
ΔHƟ H2O(l) =-285.8KJmol-1
 EFFECTS OF TEMPERATURE ON STANDARD
HEAT OF REACTION
• Standard heat of reaction; which is the heat change of a chemical reaction that
occurs at 298K and 1 atmosphere(standard conditions)
• Standard heat of reaction changes with temperature due to;
 Heat capacity; heat capacity of reactants and products varies with temperature.
 Enthalpy change; DH changes with temperature due to Cp.
• We get the it using
• DH(T2)=DH(T1)+∑(Cp(products)-Cp(reactants))DT
• From T1 to T2
• Where;
• DH(T2)= standard heat of reaction at temperature T2
• DH(T2)=standard heat of reaction at temperature T1(296K)
• DT=temperature interval
• Therefore: if Cp(product)>Cp(reactants), DH increases with temperature
if Cp(products)<Cp(reactants), DH decreases with temperature
Examples and application
• Combustion reactions
• Endothermic reactions
• Phase transitions
HEAT EFFECTS ON INDUSTRIAL REACTIONS
Heat effects on industrial reactions refers to the energy changes that
occur during chemical reaction in industrial processes.
Note; industrial reactions are rarely carried out under standard
states conditions
In actual reactions the reaction may not be present in
stoichiometric proportions, the reaction may not go to completion and
the final temperature may differ from the initial temperature.
• A reaction is referred to be adiabatic when there is no heat interaction with the
surrounding.
• If the reaction is release heat ,heat liberated is utilized to increase the enthalpy of the
products . the products are in turn heated to a higher temperature.
• When a fuel gas is heat under adiabatic conditions ,the temperature attained by the
system is referred to as the adiabatic flame temperature.
• If the reactants are fed into the reactor at a temperature ,T1 they are then cooled to
a standard temperature of 298K and then heated up to the temperature ,T the
adiabatic flame temperature
• Let  1 denote the enthalpy for cooling the temperature of reactants from T1 to 298K
and  2 denote the enthalpy for rising the temperature of the products from 298K to
temperature ,T.
• Since the entire process is adiabatic , the heat , Q=0 and so the enthalpy =0
• Then, = 1 +2 +298

1
QUESTIONS

• ) Calculate the theoretical flame temperature for CO when burned

with 100% excess air when both the reactants are at 373K. The heat
capacities (J/molK) may be assumed as 29.0 for CO ,33,03 for N2, and
53.59 for CO2 . the standard heat of combustion at 298K is -
283.1kj/mol CO.
• 2) Dry methane is burned with dry air . both are at 298K
initially .the flame temperature is 1600K.if complete combustion is
assumed ,how much excess air is being used? The standard heats of
reaction is -8.028*10^5J/mol of the reacted methane . Mean molar
specific heats of the gases between 298Kand 1600K are in J/molK.
• CO2 = 51.66, O2 = 34.01 , H2O = 40.45, N2 = 32.21