THERMOCHEMISTRY

Study of heat change in chemical

reactions
 Systems, Surroundings & Internal Energy
System = the part of the universe under study
 chemicals in a flask.
 the coffee in your coffee cup.
 my textbook.

Surroundings = rest of the universe (or as much as

needed…)
 the flask.
 perhaps the flask and this classroom.
 perhaps the flask and all of the building, etc.

Universe = System + Surroundings

 The First Law of Thermodynamics
• Thermodynamics
• Deals with all kinds of energy effects in all kinds
of processes
Two types of energy:
• Heat (q)
• Work (w)
The Law of Conservation of Energy
• ΔEsystem = - ΔEsurroundings
The First Law:
• ΔE = q + w
• The total change in energy is equal to the sum of the
heat and work transferred between the system and the
surroundings
 The First Law of Thermodynamics

Internal energy = E within the system because of

nanoscale position or motion
• Conservation of energy becomes:
ΔE = q + w
Heat
• Thermal E transfer caused by a T difference.
• Heat flows from hotter to cooler objects until they
reach thermal equilibrium (have equal T ).
 Work
• In an internal combustion engine, a significant
fraction of the energy of combustion is
converted to useful work
– The expansion of the combustion gases produces a
volume and a pressure change
– The system does work on its surroundings
• Propels the car forward
• Overcomes friction
• Charges battery
 Pressure-
Volume Work
 SURROUNDINGS

SYSTEM

Heat transfer out

Heat transfer in
q<0
q>0

ΔE = q + w

Work transfer in Work transfer out

w>0 w<0

Note the same sign convention for q and w

 SAMPLE PROBLEMS
1. A liquid cools from 45°C to 30°C, transferring 911 J
to the surroundings. No work is done on or by the
liquid. What is ΔEliquid?

2. A system does 50.2 J of work on its surroundings and

there is a simultaneous 90.1 J heat transfer from the
surroundings to the system. What is ΔEsystem?
State Functions and Path Independence
State
State functions functions
Always have the same value whenever the
system is in the same state. HE
P V
Two equal mass samples of water produced by:
T etc.
1. Heating one from 20°C to 50°C.
2. Cooling the other from 100°C to 50°C.
have identical final H (and V, P, E…).

State function changes are path independent.

ΔH = Hfinal – Hinitial is constant.
 ENTHALPY of Chemical
Reactions
• At constant V,
ΔV = 0

• At constant p,
 Enthalpy, ΔH
• H = E + PV
• ΔH = ΔE + PΔV ; ΔH = qp
– The PV product is important only where gases are
involved; it is negligible when only liquids or
solids are involved
• ΔH = ΔE + ΔngRT
– Δng is the change in the number of moles of gas as
the reaction proceeds
Measurement of Heat Flow: Calorimetry

• A calorimeter is a device used to measure the

heat flow of a reaction
– The walls of the calorimeter are insulated to block
heat flow between the reaction and the
surroundings
– The heat flow for the system is equal in magnitude
and opposite in sign from the heat flow of the
calorimeter
• qreaction = - qcalorimeter
• qreaction = - Ccal Δt
 The Calorimetry Equation
q = C x Δt
– Δt = tfinal – tinitial
– C (uppercase) is the heat capacity of the system: it is
the quantity of heat needed to raise the temperature of
the system by 1 °C
q = m x c x Δt
– c (lowercase) is the specific heat: the quantity of heat
needed to raise the temperature of one gram of a
substance by 1 °C
• c depends on the identity and phase of the
substance
 Measuring Enthalpy Changes
Coffee-cup calorimeter
Nested styrofoam cups prevent heat transfer with
the surroundings.

Constant P. ΔT measured.
q = qp = ΔH

Assume the cups do not absorb heat. (Ccal

= 0 and qcal = 0)
 Measuring Enthalpy Changes
Bomb Calorimeter
Measure ΔT of the water. Constant V: qV = ΔE

Conservation of E:
qreaction + qbomb + qwater = 0

or
−qreaction = qbomb + qwater
with
qbomb = mcalccalΔT = CcalΔT
A constant for a calorimeter
 Sample Problem
Copper is used in building the integrated
circuits, chips and printed circuit boards for
computers. When 228 J of heat are absorbed
by 125 g of copper at 22.38oC, the temperature
increases to 27.12oC. What is the specific heat
of copper?
A student wishes to determine the heat
capacity of a coffee-cup calorimeter. After she
mixes 100.0 g of water at 58.5°C with 100.0 g
of water, already in the calorimeter, at 22.8°C,
the final temperature of the water is 39.7°C.
Calculate the heat capacity of the calorimeter
in J/°C. Use 4.184 J/g - °C as the specific heat
of water.
 Measuring Enthalpy Changes
Octane (0.600 g) was burned in a bomb calorimeter containing 751 g
of water. T increased from 22.15°C to 29.12°C. Calculate the heat
evolved per mole of octane burned. Ccal = 895 J°C-1.
2 C8H18(l) + 25 O2(g) 16 CO2(g) + 18 H2O(l)

qsys + qsurr = 0
qreaction + qbomb + qwater = 0
qbomb = CcalΔT = 895 J°C-1 (29.12 – 22.15)°C = +6238 J
qwater = m c ΔT = 751 g (4.184 J g-1 °C-1)(29.12 – 22.15)°C
= +2.190 x 104 J
So −qreaction = +6238 + 2.190 x 104 J = 2.81 x 104 J = 28.1 kJ
qreaction = −28.1 kJ
 Measuring Enthalpy Changes
Octane (0.600 g) was burned in a bomb calorimeter… Calculate the heat evolved
per mole of octane burned

Molar mass of C8H18 = 114.23 g/mol.

nC8H18 = (0.600 g) / (114.23 g/mol)
= 0.00525 mol C8H18

Heat evolved /mol octane = −28.1 kJ

0.00525 mol
= −5.35 x 103 kJ/mol
= −5.35 MJ/mol
 Thermochemical Equations
• a chemical equation with the ΔH for the
reaction included
Example
NH4NO3 (s)  NH4+ (aq) + NO3- (aq) ΔH = +28.1kJ
This means:

+28.1 kJ +28.1 kJ +28.1 kJ

Or or
1 mol NH4NO3(s) 1 mol NH4+(aq) 1 mol NO3-(aq)
 Conventions for Thermochemical
Equations
1. The sign of ΔH indicates whether the reaction is
endothermic or exothermic
2. The coefficients of the thermochemical equation
represent the number of moles of reactant and
product
3. The phases of all reactant and product species
must be stated
4. The value of ΔH applies when products and reactants are at
the same temperature, usually 25 °C
 Rules of Thermochemistry
• ΔH is directly proportional to the amount of
reactant or product
– If a reaction is divided by 2, so is ΔH
– If a reaction is multiplied by 6, so is ΔH
• ΔH changes sign when the reaction is reversed
• ΔH has the same value regardless of the
number of steps
 Sample Problem

In photosynthesis, the following reaction takes place:

6CO2(g) + 6H2O(l)  6O2(g) + C6H12O6(s) H = + 2801 KJ

a. Calculate H when one mole of carbon dioxide

reacts?
b. How many kilojoules of energy are liberated when
15.00 g of glucose is burned in oxygen?
 METHODS OF DETERMINING
Hreaction

1. DIRECT METHOD
- using Hof of every reactants and products
of chemical reaction
2. INDIRECT METHOD
- using HESS LAW (for reaction involving
several steps)
 DIRECT METHOD

ΔH° ={(nproducts)(ΔHf° products)}

– {(nreactants)(ΔHf° reactants)}

Where: ΔHf° = standard molar enthalpy of

formation taken from Thermodynamic data
 Standard Molar Enthalpy of
Formation
Standard state = most stable form of the pure element
at P = 1 bar.
 e.g. C standard state = graphite (not diamond)

ΔHf° for any element in its standard state is zero.

(take 1 mol of the element and make… 1 mol of element)

ΔHf° (Br2(l) ) = 0 at 298 K

ΔHf° (Br2(g) ) ≠ 0 at 298 K
Formation reaction
Make 1 mol of compound from its elements in their
standard states.
H2 combustion:
2 H2(g) + O2(g) 2 H2O(l) ΔH° = −571.66 kJ
but the formation reaction is:
H2(g) + ½ O2(g) H2O(l)
1 ΔHf° = −285.83 kJ

f = formation
 DIRECT METHOD
ΔH° ={(nproducts)(ΔHf° products)}
– {(nreactants)(ΔHf° reactants)}
Example
Calculate ΔH° for:
CH4(g) + NH3(g)  HCN(g) + 3 H2(g)
ΔHf° : -46.11 -74.85 +134 0

ΔH° = [1ΔHf°(HCN) + 3 ΔHf°(H2)] −

[1ΔHf°(NH3) + 1ΔHf°(CH4)]

= [+134 + 3(0)] − [− 46.11 + (−74.85)] = 255 kJ

 INDIRECT METHOD - Hess’s
Law
“If the equation for a reaction is the sum of the
equations for two or more other reactions, then ΔH°
for the 1st reaction must be the sum of the ΔH° values
of the other reactions.”

Another version:
“ΔH° for a reaction is the same whether it takes place in a
single step or several steps.”

H is a state function
SAMPLE PROBLEMS