Thermochemistry

INTENDED LEARNING OUTCOMES

The students should be able to:
• Distinguish between exothermic and endothermic reactions
• Explain how calorimeter determines heats of reactions
• Explain enthalpy change
• Apply Hess’s law to determine standard enthalpy change
Thermochemistry
• The study of the changes in heat in chemical reactions
• Study of heat flow that accompanies chemical reactions
• “ thermes”- Greek word meaning heat
• Part of thermodynamics which examines energy and work in
the system
Thermodynamics
Thermodynamics
• Thermodynamics is the science of heat
(energy) transfer.

Heat energy is associated with

molecular motions.
Heat transfers until thermal equilibrium is
established.
 Energy
Energy &
& Chemistry
Chemistry
All of thermodynamics depends on the law of
CONSERVATION OF ENERGY.
• The total energy is unchanged in a chemical reaction.
• If PE of products is less than reactants, the difference
must be released as KE.
Energy
Energy Change
Change in
in Chemical
Chemical Processes
Processes
PE

Reactants
Kinetic
Energy

Products

PE of system dropped. KE increased. Therefore, you often

feel a T increase.
Heat is the transfer of thermal energy between two bodies
that are at different temperatures.
HEAT is the form of energy that flows between 2 objects
because of their difference in temperature.
Thermal energy is the energy associated with the random
motion of atoms and molecules

Temperature is a measure of the thermal energy.

6.2
Heat
• Heat: Form of energy
• Transferred from a body at a high temperature to one at a
lower temperature when they are brought in contact with
each other
Heat Flow
• System: Part of the universe on which attention is
focused
• Reactants and products after a chemical reaction
• Surroundings: Rest of the universe
• Materials in close contact with the system are
considered
The system is the specific part of the universe that is of interest
in the study.
SURROUNDINGS
SYSTEM

open closed isolated

Exchange: mass & energy energy nothing
6.2
 Exothermic reaction
Heat transfers from SYSTEM to SURROUNDINGS.

T(system) goes down

T(surr) goes up
 Endothermic Reaction
Heat transfers from SURROUNDINGS to the SYSTEM.

T(system) goes up
T (surr) goes down
 Exothermic reaction is any process that gives off heat – transfers
thermal energy from the system to the surroundings.

2H2 (g) + O2 (g) 2H2O (l) + energy

H2O (g) H2O (l) + energy

Endothermic reaction is any process in which heat has to be supplied

to the system from the surroundings.

energy + 2HgO (s) 2Hg (l) + O2 (g)

energy + H2O (s) H2O (l)

6.2
Direction and Sign of Heat Flow

• Symbol - q
• q is positive when heat flows into the system from the surroundings
• q is negative when heat flows from the system into the surroundings
• Endothermic processes (q > 0) have positive q
• H 2 O  s   H 2O  
• Exothermic processes (q < 0) have negative q
CH 4  g   2O 2  g   CO 2  g   2H 2O  
Magnitude of Heat Flow
• q is expressed in joules and kilojoules
• Unit used in the past was calorie
• 1 calorie = 4.184 J
• 1 kilocalorie = 4.184 kJ
• Nutritional calories are expressed in kcal
HEAT CAPACITY(C)
The heat capacity (C) of a substance is the amount of
heat (q) required to raise the temperature of a given
quantity (m) of the substance by one degree Celsius.
The heat required to raise an object’s T by 1 ˚C.
The specific heat (s) of a substance is the amount of heat
(q) required to raise the temperature of one gram of the
substance by one degree Celsius.

C = ms
Heat (q) absorbed or released:
q = msDt
q = CDt
Dt = tfinal - tinitial
6.4
 Specific
Specific Heat
Heat Capacity
Capacity
How much energy is transferred due to T
difference?
The heat (q) “lost” or “gained” is related to
a) sample mass
b) change in T and
c) specific heat capacity
Specific
= he
heat lost
(mass,
g)(T
K)ch
 Specific
Specific Heat
Heat Capacity
Capacity
Substance Spec. Heat (J/g•K)
H2O 4.184
Ethylene glycol 2.39
Al 0.897
glass 0.84

Aluminum
 Specific
Specific Heat
Heat Capacity
Capacity
If 25.0 g of Al cool from 310 oC to 37 oC, how
many joules of heat energy are lost by the
Al?

Specific
= he
heat lost
(mass,
g)(TK)ch
 Specific
Specific Heat
Heat Capacity
Capacity
If 25.0 g of Al cool from 310 oC to 37 oC, how many joules of heat energy are lost by the Al?

heat gain/lose = q = (sp. ht.)(mass)(∆T)

where ∆T = Tfinal - Tinitial

q = (0.897 J/g•K)(25.0 g)(37 - 310)K
q = - 6120 J

Notice that the negative sign on q signals

heat “lost by” or transferred OUT of Al.
CALORIMETRY
• Measurement of the amount of heat released or
absorbed during a chemical reaction
• Calorimetry experiments determine the heats
( enthalpy changes) of reactions by making accurate
measurements of temperature changes produced in a
calorimeter.
Calor – Latin word for heat
Measuring Heat Flow
• Calorimeter
• Device used to measure the heat flow of a reaction
• Walls are insulated to block exchange of heat with the surrounding air
• Heat flow for the system is:
• Equal in magnitude
• Opposite in sign to that of the calorimeter

qreaction =  qcalorimeter
q cal  C cal  t
 Constant-Pressure Calorimetry

qsys = qwater + qcal + qrxn

qsys = 0

qrxn = - (qwater + qcal)

qwater = msDt
qcal = CcalDt

Reaction at Constant P
DH = qrxn

No heat enters or leaves!

6.4
Coffee-Cup Calorimeter
• Polystyrene is a good insulator
• Heat evolved from reaction is absorbed by the water
• Heat capacity of the coffee-cup calorimeter is that
of water
• For a reaction performed in a coffee-cup calorimeter

J
q reaction =  mass H2O  4.18  t
g C 
Measuring Heat Flow
 q reaction  0 
• If the reaction is exothermic
• qcalorimeter must be positive
• Converse if the reaction is endothermic
• Basic calorimetric measurement equation
• To calculate amount of heat absorbed in a reaction
• Must know the heat capacity and temperature change
Example 8.2
• Calcium chloride, CaCl2, is added to canned vegetables to
maintain the vegetables’ firmness. When added to water, it
dissolves
CaCl2  s   Ca  aq   2Cl  aq 
2 

• A calorimeter contains 50.0 g of water at 25.00°C. When 1.00

g of calcium chloride is added to the calorimeter, the
temperature rises to 28.51°C. Assume that all the heat given
off by the reaction is transferred to the water
• Calculate q for the reaction system
Example 8.2
t
• Solution:
t = t final  t initial  28.51C  25.00C = 3.51C
qH 2 O
qH2O  mass  t  c =  50.0 g   4.18 J/g  C   3.51 C 
 734 J
qreaction
qreaction =  qH 2O  734 J
• Since the final temperature is larger than the initial
temperature after the addition of CaCl2, the reaction must
be exothermic
• Thus qreaction must be negative
Problems:
1. The calorimeter is filled with 75.0g of water at an initial
temperature of 19.8 oC. A 0.050 mole sample of solid
NaOH is added and the temperature increases to 26.7 oC.
Determine the heat of reaction and enthalpy change.
2. When a 4.25 g sample of solid NH4NO3 dissolved in 60.0g
of water in a calorimeter, the temperature drops from
21.00C to 16.9 oC. Calculate the heat of reaction and
enthalpy change for the solution process.
PROBLEMS
3. When a 13.7 g sample of solid Pb(NO3)2 dissolves in 85.0 g
of water in a calorimeter, the temperature drops from 23.4 oC
to 19.7 oC. Calculate the heat of reaction and enthalpy change
for the solution process.
4. What is the specific heat of nickel if the temperature of a
32.2 g sample of Ni is increased by 3.5 oC when 50J of heat is
added?
 Calorimetry


qreaction   qcalorimeter  qH2O 
Some heat from reaction warms
water
qwater = (sp. ht.)(water mass)(∆T)

Some heat from reaction warms

“bomb”
q calorim eter  C cal   t

Total heat evolved = qtotal = qwater + qbomb

 Measuring
Measuring Heats
Heats of
of Reaction
Reaction
CALORIMETRY
CALORIMETRY

Calculate heat of combustion of octane.

C8H18 + 25/2 O2 --> 8 CO2 + 9 H2O
•Burn 1.00 g of octane
• Temp rises from 25.00 to 33.20 oC
• Calorimeter contains 1200 g water
• Heat capacity of bomb = 837 J/oC
 Measuring
Measuring Heats
Heats of
of Reaction
Reaction
CALORIMETRY
CALORIMETRY
Step 1 Calc. heat transferred from reaction to water.
q = (4.184 J/g•oC)(1200 g)(8.20 oC) = 41,170 J

Step 2 Calc. heat transferred from reaction to bomb.

q = (bomb heat capacity)(∆T)
= (837 J/oC)(8.20 oC) = 6860 J

Step 3 Total heat evolved

41,170 J + 6860 J = 48,030 J
Heat of combustion of 1.00 g of octane = - 48.0 kJ
ENTHALPY ( H )
• used to quantify the heat flow into or out of a system in a
process that occurs at constant pressure
• Heat content of a system at constant pressure
• Depends on its temperature, physical state and composition
ENTHALPY CHANGE (DH)
• When the pressure remains constant, the heat absorbed or released
during chemical reaction is equal to the enthalpy change for the
reaction.

DH = heat given off or absorbed during a reaction at constant pressure

• Written as enthalpy of product minus enthalpy of reactant

DH = H (products) – H (reactants)
Hproducts < Hreactants Hproducts > Hreactants
DH < 0 DH > 0
 Thermochemical Equations

Is DH negative or positive?

System absorbs heat

Endothermic

DH > 0

6.01 kJ are absorbed for every 1 mole of ice that

melts at 00C and 1 atm.

H2O (s) H2O (l) DH = 6.01 kJ

6.3
 Thermochemical Equations

System gives off heat

Exothermic

DH < 0

890.4 kJ are released for every 1 mole of methane that is

combusted at 250C and 1 atm.

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH = -890.4 kJ

6.3
 ENTHALPY
∆H = Hproduct - Hreactant

IfIf H
Hproduct > H reactant then
then ∆H
∆H is
is positive
product > Hreactant positive
Process is ENDOTHERMIC
Process is ENDOTHERMIC

IfIf H
Hproduct < H reactant then
then ∆H
∆H is
is negative
product < Hreactant negative
Process is EXOTHERMIC
Process is EXOTHERMIC
 Thermochemical Equations

• The stoichiometric coefficients always refer to the number

of moles of a substance
H2O (s) H2O (l) DH = 6.01 kJ

• If you reverse a reaction, the sign of DH changes

H2O (l) H2O (s) DH = -6.01 kJ
• If you multiply both sides of the equation by a factor n,
then DH must change by the same factor n.

2H2O (s) 2H2O (l) DH = 2 x 6.01 = 12.0 kJ

6.3
6.4
 Thermochemical Equations

• The physical states of all reactants and products must be

specified in thermochemical equations.
H2O (s) H2O (l) DH = 6.01 kJ
H2O (l) H2O (g) DH = 44.0 kJ

How much heat is evolved when 266 g of white

phosphorus (P4) burn in air?
P4 (s) + 5O2 (g) P4O10 (s) DH = -3013 kJ

1 mol P4 3013 kJ
266 g P4 x x = 6470 kJ
123.9 g P4 1 mol P4

6.3
Example 8.4
Bunsen burners in your labs are fueled by natural gas, which is mostly
methane, CH4
The thermochemical equation for the combustion (burning in oxygen) of
methane is

CH 4  g   2O 2  g   CO 2  g   2H 2 O  
H =  890.3 k/J
Calculate ∆H when 5.00 g of CH4 react with an excess of oxygen
SOLUTION
• ∆H

1 mol CH 4 -890.3 kJ
5.00 g CH 4 × × = -278 kJ
16.04 g CH 4 1 mol CH 4
Problem
• Given

2H 2  g  + O 2  g   2H 2O   H=  571.6 k/J

• Calculate ∆H for the equation

1
H 2 O    H 2  g   O 2  g 
2
Solution

2H 2 O    2H 2  g   O2  g 
H    571.6 kJ   571.6 kJ
1
H 2 O    H 2  g   O 2  g 
2
1
H =  571.6 kJ   285.8 kJ
2
HESS’S LAW
• If the series of reactions are added together, the enthalpy change for the
reaction will be the sum of enthalpy changes for the individual steps

• if two or more chemical equations can be added together to

produce an overall equation, the sum of the enthalpy equals the
enthalpy change of the overall equation.

This is called the Heat of Summation, ∆H

Hess’s Law
• When reactants are converted to products, the change in
enthalpy is the same whether the reaction takes place in one
step or in a series of steps.

• the heat evolved or absorbed in a chemical process is the same

whether the process takes place in one or several steps
Strategy in solving problems
• Read through the whole question
• Plan a Strategy
• Evaluate the given equations.
• Rearrange and manipulate the equations so that they will produce the
overall equation.
• Add the enthalpy terms.
Hess’s Law
• If a reaction is carried out in a series of steps, ΔH is the sum of all
the enthalpy changes
CH4(g) + O2(g) → CO2(g) + 2H2O(g) ΔH=-802
2H2O(g) → 2H2O(l) ΔH=-88
------------------------------------------------------------
CH4(g) + O2(g) → CO2(g) + H2O(l) ΔH=-890
H2O(g) + C(s) → CO(g) + H2(g)
Example 1

• Use these equations to calculate the molar enthalpy change

which produces hydrogen gas.
• C(s) + ½ O2(g) → CO(g) ∆H = -110.5kJ
• H2(g) + ½ O2(g) → H2O(g) ∆H = -241.8kJ
H2O(g) + C(s) → CO(g) + H2(g)

• Use these equations to calculate the molar enthalpy change

which produces hydrogen gas.
• C(s) + ½ O2(g) → CO(g) ∆H = -110.5kJ
• H2O(g) → H2(g) + ½ O2(g)∆H = +241.8kJ
_____________________________________
C(s) + H2O(g) → H2(g) + CO(g) ∆H=+131.3kJ
 Determine the heat of reaction for the reaction:
4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)

Using the following sets of reactions:

N2(g) + O2(g)  2NO(g) H = 180.6 kJ

N2(g) + 3H2(g)  2NH3(g) H = -91.8 kJ

2H2(g) + O2(g)  2H2O(g) H = -483.7 kJ

Hint: The three reactions must be algebraically

manipulated to sum up to the desired reaction.
and.. the H values must be treated accordingly.
54
Goal: 4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)
Using the following sets of reactions:
N2(g) + O2(g)  2NO(g) H = 180.6 kJ
N2(g) + 3H2(g)  2NH3(g) H = -91.8 kJ
2H2(g) + O2(g)  2H2O(g) H = -483.7 kJ

NH3: Reverse and x 2 4NH3  2N2 + 6H2 H = +183.6 kJ

O2 : Found in more than one place, SKIP IT (its hard).
NO: x2 2N2 + 2O2  4NO H = 361.2 kJ
H2O: x3 6H2 + 3O2  6H2O H = -1451.1 kJ

55
 Goal: 4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)

NH3: Reverse and x2 4NH3  2N2 + 6H2 H = +183.6 kJ

O2 : Found in more than one place, SKIP IT.
NO: x2 2N2 + 2O2  4NO H = 361.2 kJ
H2O: x3 6H2 + 3O2  6H2O H = -1451.1 kJ

Cancel terms and take sum.

4NH3 + 5O2  4NO + 6H2O H = -906.3 kJ

Is the reaction endothermic or exothermic?

56
Standard enthalpy of formation (DHf0)
• the heat change that results when one mole of a
compound is formed from its elements at a pressure of
1 atm.
• an arbitrary scale established as a reference point for all
enthalpy expressions.

• The standard enthalpy of formation of any element in its

most stable form is zero.

DH0f (O2) = 0 DH0f (C, graphite) = 0

DH0f (O3) = 142 kJ/mol DH0f (C, diamond) = 1.90 kJ/mol
6.5
6.5
STANDARD HEAT OF REACTION (DH 0
rxn )
The heat of reaction is based on the standard state.
• For a gas, the standard state is 1 atm with the gas behaving ideally
• For a substance in aqueaous solution, the standard state is 1 M
• For pure substance(element or compound), the standard state is
usually the most stable form of the substance at 1 atm and
temperature is 298K
The standard enthalpy of reaction (DH0rxn) is the
enthalpy of a reaction carried out at 1 atm.
aA + bB cC + dD

DHrxn
0
= [ cDH0f (C) + dDH0f (D) ] - [ aDH0f (A) + bDH0f (B) ]

(Enthalpy is a state function. It doesn’t matter how you get

there, only where you start and end.)
6.5
Problem 1:
Nitric acid is used to make many products, including fertilizers, dyes and
explosives. The first step in the production is the oxidation of
ammonia:
4NH3(g) + 5O2(g) → 4NO(g) + 6H20(g)

Calculate the standard heat of reaction DH0 rnx from the DHf0 values
Problem 2:
• Given the combustion of methanol:
CH3OH + 3/2O2 → CO2 + 2H2O D H0 combustion = -638.5kJ

Determine the heat of formation of methanol at standard state.

 Thermodynamics
State functions are properties that are determined by the state
of the system, regardless of how that condition was achieved.
energy, pressure, volume, temperature

Potential energy of hiker 1 and hiker 2

is the same even though they took
different paths.
6.7
Thermodynamics
• Deals with energy effects in all kinds of processes
• Distinguishes between energy types
• Heat (q)
• Work (w)
• Law of conservation of energy: Energy can neither be created nor
destroyed; it can only be transferred between systems and
surroundings

E s y s te m  E s u rro u n d in g s
INTERNAL ENERGY, E
• The sum of the kinetic and potential energies of all particles in the
system
DE = Eproducts – Ereactants

Losing some energy to surroundings

DE 0 Efinal  Einitial
Gaining some energy from surroundings
DE 0 Efinal  Einitial
First Law of Thermodynamics
• Total change in energy of a system is equal to the sum of the heat
and work transferred between the system and the surroundings.

E = q + w
• Heat(q) – energy transferred between system and surroundings as
a result of difference in their temperature
• Work(w) – energy transferred when an object is moved by force.
 FIRST
FIRST LAW
LAW OF
OF
THERMODYNAMICS
THERMODYNAMICS
heat energy transferred

∆E = q + w work done
by the
energy system
change

Energy is conserved!
Conventions
• q and w are positive
• When the heat or work enters the system from the
surroundings
• q and w are negative
• When the heat or work leaves the system for the
surroundings
heat transfer in heat transfer out
(endothermic), +q (exothermic), -q

SYSTEM

∆E = q + w

w transfer in w transfer out

(+w) (-w)
 Enthalpy and the First Law of Thermodynamics
DE = q + w
At constant pressure, q = DH and w = -PDV
DE = DH - PDV
DH = DE + PDV

6.7
• Calculate ∆E of a gas for a process in which the gas
• Absorbs 20 J of heat and does 12 J of work by expanding
• Evolves 30 J of heat and has 52 J of work done on it as it
contracts
• Solution:
• Signs for w and q, ∆E
• w is negative (work is done by the system)
• q is positive (heat is absorbed)
E = q + w = 20J +  12 J   8 J

• Signs for w and q, ∆E

• w is positive (work is done on the system; enters the
system)
• q is negative
E = q +(heat
w = is evolved)
 30 J + 52 J = 22 J