Thermodynamics
Calorimetry: The Experimental Measurement of Heat
Outline
• Background
• Exothermic vs Endothermic Reactions
• Heat Capacity
• Specific Heat
• Specific Heat of Selected Substances and Mixtures
• Relevance
Background
Thermodynamics: Study of interactions among work, energy, and
heat
Calorimetry: Experimental measurement of heat
How did they first measure heat?
• Antoine Lavoisier (1782)
• World’s first ice-
calorimeter
• Published in his book
“Elements of
Chemistry”
Exothermic vs. Endothermic
Reactions
EXOTHERMIC ENDOTHERMIC
Reaction that gives off heatReaction that absorbs heat
to its surroundings from its surroundings
• A candle flame • Forming cation from atom in gas
• Burning sugar phase
• Rusting iron • Producing sugar by photosynthesis
• Making ice cubes • Cooking an egg
• Forming bonds • Melting ice cubes
• Breaking bonds
Pop
Is evaporation of water H2O (l) H2O(g) an endothermic or exothermic
Quiz!
reaction?
Difference between Heat &
Temperature
TEMPERATURE HEAT
It is the measure of average It is the transfer of energy
K.E energy in an object . between Objects with
different Temperature .
Units are K , C Or F Unit is Joule or Calories
Temperature is intensive Heat is Extensive quantity .
quantity .
Specific Heat
• Specific Heat (denoted by letter “Cp”)
• Measurement of the amount of heat required to change a
substance’s temperature of 1 gram of substance by 1K.
Cp = q
or
DT m
C= Heat Capacity (J/ g K)
Calculate the heat absorbed by 50.0 g of Cu(s) as it q= quantity of heat
changes its temperature from 300 K to 500K. transferred
m= mass
3,850J DT= temperature change
3850 joules of heat are absorbed by
Cu(s)
Specific Heats of Selected Substances and
Mixtures
Substance Cp (J/g K)
Ag(s) 0.235
Al (s) 0.897
Au(s) 0.129
Ca(s) 0.647
Cp(Ag) < Cp (H2O)
CaCO3 (s) 0.920 Cp (metal ) < Cp (nonmetal)
Cu(s) 0.385
Small specific heat= substance
Fe(s) 0.449 translate heat transfer to
relatively large temperature
H2O (s) 2.06 change
H2O (l) 4.19
H2O (g) 2.02
Relevance
How do these work?
THERMODYNAMICS - ENTHALPY CHANGES
Enthalpy a measure of the heat content of a substance at constant pressure
you cannot measure the actual enthalpy of a substance
you can measure an enthalpy CHANGE
written as the symbol DH , “delta H ”
Enthalpy change (DH) = Enthalpy of products - Enthalpy of reactants
ENTHALPY
ENTHALPY
REACTION CO-ORDINATE REACTION CO-ORDINATE
Enthalpy of reactants > products Enthalpy of reactants < products
DH = - ive DH = + ive
EXOTHERMIC Heat given out ENDOTHERMIC Heat absorbed
STANDARD ENTHALPY CHANGES
Why a
standard? enthalpy values vary according to the conditions
a substance under these conditions is said to be in its standard state ...
Pressure:- 100 kPa (1 atmosphere)
A stated temperature usually 298K (25°C)
• as a guide, just think of how a substance would be under normal lab conditions
• assign the correct subscript [(g), (l) or (s) ] to indicate which state it is in
• any solutions are of concentration 1 mol dm-3
• to tell if standard conditions are used we modify the symbol for DH .
Enthalpy Change Standard Enthalpy Change
(at 298K)
STANDARD ENTHALPY OF FORMATION
Definition The enthalpy change when ONE MOLE of a compound is formed in its
standard state from its elements in their standard states.
Symbol DH°f
Values Usually, but not exclusively, exothermic
Example(s) C(graphite) + O2(g) ———> CO2(g)
H2(g) + ½O2(g) ———> H2O(l)
2C(graphite) + ½O2(g) + 3H2(g) ———> C2H5OH(l)
Notes Only ONE MOLE of product on the RHS of the equation
Elements In their standard states have zero enthalpy of formation.
Carbon is usually taken as the graphite allotrope.
STANDARD ENTHALPY OF COMBUSTION
Definition The enthalpy change when ONE MOLE of a substance undergoes complete
combustion under standard conditions. All reactants and products are in
their standard states.
Symbol DH°c
Values Always exothermic
Example(s) C(graphite) + O2(g) ———> CO2(g)
H2(g) + ½O2(g) ———> H2O(l)
C2H5OH(l) + 3O2(g) ———> 2CO2(g) + 3H2O(l)
Notes Always only ONE MOLE of what you are burning on the LHS of the equation
To aid balancing the equation, remember...
you get one carbon dioxide molecule for every carbon atom in the original
and one water molecule for every two hydrogen atoms
When you have done this, go back and balance the oxygen.
HESS’S LAW
“The enthalpy change is independent of the path taken”
How The enthalpy change going from
A to B can be found by adding the
values of the enthalpy changes for
the reactions A to X, X to Y and Y to B.
DHr = DH1 + DH2 + DH3
If you go in the opposite direction of an arrow, you subtract the value of
the enthalpy change.
e.g. DH2 = - DH1 + DHr - DH3
The values of DH1 and DH3 have been subtracted because the route
involves going in the opposite direction to their definition.
HESS’S LAW
“The enthalpy change is independent of the path taken”
Use applying Hess’s Law enables one to calculate enthalpy changes from
other data, such as...
changes which cannot be measured directly e.g. Lattice Enthalpy
enthalpy change of reaction from bond enthalpy
enthalpy change of reaction from DH°c
enthalpy change of formation from DH°f
