CHAPTER 6: THERMOCHEMISTRY
6.1 The Nature of Energy
● Energy: The capacity to do work or produce heat
Potential Energy: energy due to position or composition
Kinetic Energy: energy due to the motion of the object (KE= ½mv2)
● Law of Conservation of energy:
Energy can neither be created nor destroyed, but can be converted
between forms
The 1st Law of Thermodynamics: Total energy of the universe is constant
Heat vs. Temperature
Temperature reflects the random motions of particles, hence the KE of the
system
Heat involves the transfer of energy between 2 objects because of temp.
difference
6.2 Enthalpy and Calorimetry
Enthalpy (H)
H = E + PV
At constant pressure, the change in enthalpy ∆H of the system is equal to
the energy flow as heat.
For chemical reactions, the enthalpy change is given by the following
equation:
∆H = Hproducts - Hreactants = qp
∆H is positive when:
● enthalpy of products is greater than that of reactants
● heat is absorbed by the system
● reaction is endothermic
∆H is negative when:
● enthalpy of products is less than that of reactants
● heat is released by the system
● reaction is exothermic
Example #1
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ∆H = -890 kJ
How much heat is released when 4.50 g of methane gas is burned?
Example #2
2 Mg(s) + O2(g) 2MgO
(s) ∆H = -1204 kJ
(a) Is this reaction exothermic or endothermic?
(b) Calculate the amount of heat transferred when 2.4 g of Mg reacts.
(c) How many grams of MgO are produced during an enthalpy change of
96.0kJ?
(d) How many kJ of heat are transferred when 7.50 g of MgO are
decomposed?
Calorimetry
The amount of heat absorbed or released during a physical or chemical
change can be measured ……..… usually by the change in temperature of a
known quantity of water
Specific heat capacity
the energy needed to raise the temp. of one gram of substance by 1°C
(units are in J/°C·g or J/K·g)
Molar heat capacity
Simply the same as above only per mole of substance ( units are J/°C·mol
or J/K·mol)
Substance Specific Heat (J/g·K)
Water (liquid) 4.18
Water (solid) 2.06
Aluminum (solid) 0.897
Iron (solid) 0.449
How can we calculate heat transfer?? q= s · m · ∆T
q= energy released or absorbed
s= specific heat capacity of substance
m= mass of substance
∆T = change in temperature
Example #3
(a) How much heat is needed to warm 250 g of water from 22°C to 98°C?
(b) What is the molar heat capacity of water?
Example #3½
#61 on page 250b
Constant Pressure Calorimetry (Styrofoam cup)
We assume the calorimeter perfectly prevents the gain or loss of heat from
solution to surroundings, the heat gained by the solution must be produced from
the chemical reaction.
Example #4
A student mixes 50. mL of 1.0 M HCl and 50. mL of 1.0M NaOH in a calorimeter
and the solution increases from 21.0°C to 27.5°C. Calculate ∆H for the
neutralization reaction below.
HCl + NaOH → NaCl + HOH ∆H = ?
Assume the calorimeter is perfect (does not lose or gain heat), the total volume of
solution is 100. mL, the solutions density is 1.0g/mL, and the solutions specific
heat is 4.18 J/g·K.
Example #5
When 50.0mL of 0.100 M AgNO3 and 50.0 mL of 0.100 M HCl are mixed the
temperature increases from 22.30°C to 23.11°C.
The rxn is: AgNO3(aq) + HCl(aq) AgCl(s) + HNO3(aq)
Calculate ∆H for this reaction, assume that combined solution has a mass of 100.0
g and specific heat of 4.18 J/g·°C.
Bomb Calorimeter (Constant Volume)
● used to study combustion reactions
● designed to withstand high pressure
● to calculate the heat of combustion, it is necessary to know the heat
capacity of the calorimeter, ccal
qrxn = -ccal · ∆T
Example #6
CH6N2 is used as liquid rocket fuel. The combustion of this with oxygen produces
N2(g), CO2(g), and water.
When 4.00 g of CH6N2 is combusted in a bomb calorimeter, the temp. of
calorimeter increases from 25.00°C to 39.50°C. (ccal is 7.794 kJ/°C) What is the
heat of reaction for the combustion of one mole of CH6N2.
6.3 Hess’s Law
In going from a particular set of reactants to a particular set of products, the
change in enthalpy is the same whether the reaction takes place in one step or a
series of steps.
To use Hess’s law must understand 2 characteristics about ∆H for a reaction:
1. If reaction is reversed, the sign of ∆H is reversed
2. The magnitude of ∆H is directly proportional to the quantities of reactants and
products in rxn. If coefficients are multiplied by integer so must the ∆H.
Example #1
Calculate the ∆H for the combustion of methane(CH4):
CH4 + 2 O2 CO2 + 2 H2O
Reactions ∆H
C + 2H2 CH4 -74.80 kJ
C + O2 CO2 -393.50 kJ
H2 + ½ O2 H2O -285.83 kJ
Example #2
Calculate the ∆H for the reaction:
2 C(s) + H2(g) C2H2(g)
given the following rxn’s and their enthalpy changes:
C2H2(g) + 5/2 O2(g) 2CO2(g) + H2O(l) ∆H = -1299.6 kJ
C(s) + O2(g) CO2(g) ∆H = -393.5 kJ
H2(g) + ½ O2(g) H2O(l) ∆H = -285.8 kJ
6.4 Standard Enthalpies of Formation
When the value of ∆H can’t be obtained through calorimetry we can use ….
Standard enthalpy of formation (∆Hf°) –
● change in enthalpy that accompanies the formation of one mole of a
compound from its elements with substance in standard state
● elements in their standard states are not included in the ∆Hrxn calculations.
That is, ∆Hf° for an element in its standard state is ZERO.
● Look at appendix four on page A21-A23 in textbook
∆H°rxn = ∑np∆Hf° (products) - ∑nr∆Hf°(reactants)
Example #1
CaCO3(s) → CaO(s) + CO2(g) ∆H°rxn = ?
Example #2
Calculate the ∆H°rxn for the combustion of 1 mol of bezene (C6H6)(l). (the ∆Hf° for
benzene is 49.0 kJ/mol)
