Thermochemistry

Chapter 6

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 Contents
6. 1 The Nature of Energy and Types of Energy
6. 2 Energy Changes in Chemical Reactions
6. 3 Introduction to Thermodynamics
6. 4 Enthalpy of Chemical Reactions
6. 5 Calorimetry
6. 6 Standard Enthalpy of Formation and Reaction
 Chemical Reactions

Follow two fundamental laws:

• Law of conservation of mass
• Law of conservation of energy
Energy is the capacity to do work
• Radiant energy comes from the sun and is
earth’s primary energy source
• Thermal energy is the energy associated with
the random motion of atoms and molecules
• Chemical energy is the energy stored within the
bonds of chemical substances
• Nuclear energy is the energy stored within the
collection of neutrons and protons in the atom
• Potential energy is the energy available by virtue
of an object’s position

6.1
 Energy Changes in Chemical Reactions

Heat is the transfer of thermal energy between

two bodies that are at different temperatures.

Temperature is a measure of the

thermal energy.

Temperature = Thermal Energy

5
 Thermochemistry
Study of heat change in chemical reactions.
The system is the specific part of the universe that is of
interest in the study.
The surroundings are the rest of the universe outside the
system

open closed isolated

Exchange: mass & energy energy nothing
6.2
 Exothermic process is any process that gives off heat –
transfers thermal energy from the system to the surroundings.
• Causes surrounding to warm up
2H2 (g) + O2 (g) 2H2O (l) + energy

H2O (g) H2O (l) + energy

Endothermic process is any process in which heat has to be

supplied to the system from the surroundings.
• Causes system to warm up

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

energy + H2O (s) H2O (l)

6.2
Schematic of Exothermic and Endothermic Processes

6.2
 Thermodynamics is the scientific study of the interconversion
of heat and other kinds of energy.

State functions are properties that are determined by the state

of the system, regardless of how that condition was achieved.
energy, pressure, volume, temperature,

E = Efinal - Einitial
P = Pfinal - Pinitial

Potential energy of hiker 1 and hiker 2
is the same even though they took
different paths.
V = Vfinal - Vinitial
T = Tfinal - Tinitial
All above are state functions
They are not dependent how
you got them
 First law of thermodynamics – energy can be
converted from one form to another, but cannot
be created or destroyed.
Esystem + Esurroundings = 0
or
Esystem = -Esurroundings

C3H8 + 5O2 3CO2 + 4H2O

Exothermic chemical reaction!

Chemical energy lost by combustion = Energy gained by the surroundings

system surroundings 6.3
 Another form of the first law for Esystem
E = q + w
E is the change in internal energy of a system
q is the heat exchange between the system and the surroundings
w is the work done on (or by) the system
w = -PV when a gas expands against a constant external pressure

6.3
 Work Done On the System
w=Fxd

w = -P V
V > 0
F
PxV= x d 3
=Fxd=w -PV < 0
d2

wsys < 0

Work is
not a
state
function.
w = wfinal - winitial

6.3
initial final
A sample of nitrogen gas expands in volume from 1.6 L to 5.4 L
at constant temperature. What is the work done in joules if the
gas expands (a) against a vacuum and (b) against a constant
pressure of 3.7 atm?

w = -P V

(a) V = 5.4 L – 1.6 L = 3.8 L P = 0 atm

W = -0 atm x 3.8 L = 0 L•atm = 0 joules

(b) V = 5.4 L – 1.6 L = 3.8 L P = 3.7 atm

w = -3.7 atm x 3.8 L = -14.1 L•atm

101.3 J = -1430 J
w = -14.1 L•atm x
1L•atm
6.3
 Question
• When 2.5 mole of H2O vaporizes at 1.0 atm and 25°C how much work will
be done, in joules. (1 L·atm = 101.3 J) w = -P V

6.2 kJ
Enthalpy and the First Law of Thermodynamics
E = q + w
At constant pressure:
q = H and w = -PV
E = H - PV
H = E + PV

6.3
 Question
A gas is allowed to expand, at constant temperature, from a volume of 1.0 L
to 10.1 L against an external pressure of 0.50 atm. If the gas absorbs 250 J
of heat from the surroundings, what are the values of q, w, and E?
(1 L·atm = 101.3 J)
E = q + w E = H - PV H = E + PV
All blue values/equations you should know.

q = 250 J, w = -460 J, E = -210 J

Enthalpy (H) is used to quantify the heat flow into or out of a
system in a process that occurs at constant pressure.
H = H (products) – H (reactants)
H = heat given off or absorbed during a reaction at constant pressure

Hproducts >Hreactants Hproducts < Hreactants

H > 0 H < 0 6.4
 Thermochemical Equations

Is H negative or positive?

System absorbs heat

Endothermic

H > 0

6.01 kJ are absorbed for every 1 mole of ice that

melts at 00C and 1 atm.

H2O (s) H2O (l) H = +6.01 kJ

6.4
 Thermochemical Equations

Is H negative or positive?

System gives off heat

Exothermic

H < 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) H = -890.4 kJ

6.4
 Thermochemical Equations

• The stoichiometric coefficients always refer to the number

of moles of a substance
H2O (s) H2O (l) H = +6.01 kJ Endothermic

• If you reverse a reaction, the sign of H changes

H2O (l) H2O (s) H = -6.01 kJ Exothermic

• If you multiply both sides of the equation by a factor n,

then H must change by the same factor n.

2H2O (s) 2H2O (l) H = 2 x 6.01 = 12.0 kJ

6.4
 Thermochemical Equations
• The physical states of all reactants and products must be
specified in thermochemical equations.
H2O (s) H2O (l) H = 6.01 kJ
H2O (l) H2O (g) H = 44.0 kJ

How much heat is evolved when 266 g of white

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

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

6.4
 Question
Consider following combustion reaction:
2C4H10(g) + 13O2(g)  8CO2(g) + 10H2O(l) H°rxn = –5,314 kJ
What is the heat of combustion per gram of C4H10? (MM of C4H10 is
58.12 g/mol)

–45.8 kJ/g
 A Comparison of H and E

2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) H = -367.5 kJ/mol

E = H - PV At 25 oC, 1 mole H2 = 24.5 L at 1 atm
PV = 1 atm x 24.5 L = 24.5 atm. L x 101.3 J/1 L. atm. = 2.48 kJ

E = -367.5 kJ/mol – 2.48 kJ/mol = -370. kJ/mol

6.4
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.
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.
C=mxs

Heat (q) absorbed or released:

q = m x s x t
q = C x t
t = tfinal - tinitial

6.5
How much heat is given off when an 869 g iron bar cools
from 940C to 50C? Specific heat of iron is 0.444 J/g • 0C

s of Fe = 0.444 J/g • 0C

t = tfinal – tinitial = 50C – 940C = -890C

q = mst = 869 g x 0.444 J/g • 0C x –890C = -34,000 J

Note the – sign: heat is given off, it leaves the system

(the iron bar in this case)

6.5
 Question
• Calculate the amount of heat necessary to raise the temperature of 12.0
g of water from 15.4°C to 93.0°C. The specific heat of water = 4.18
J/g·°C. q = mst

3,890 J
 Calorimetry
• Calorimetry is the experimental technique to measure heat effects of chemical
reactions or physical changes (e.g. phase change, liquid to gas (evaporation),
solid to liquid (melting), gas to liquid (condensation), etc.

• The instrument used is called a calorimeter.

• An adiabatic calorimeter is a calorimeter that is insulated from the outside, there

is no heat coming in or going out, qtotal = 0 -- here qtotal means change in the
heat is zero.

• Therefore, in an adiabatic calorimeter qrxn = – qcalorimeter. For instance, in an

exothermic reaction, the heat given off by the reaction, qrxn = – ve, therefore
qcalorimeter = +ve, the calorimeter + contents heats up.

• qcalorimeter = CΔT = –qrxn C = the calorimeter constant – heat

caparity of the calrimeter (J/K =J/oC)

• In an open adiabatic calorimeter qrxn = qp,rxn = ΔHrxn = –CΔT

6.5
 Constant-Volume Bomb Calorimetry

Qbomb = qcal = heat of calrimeter

qsys = qwater + qcal + qrxn

qsys = 0 - no change of heat in system
qrxn = - (qwater + qcal)
qwater = m x s x t
qcal = Ccal x t

Reaction at Constant V
H = qrxn
H ~ qrxn

No heat enters or leaves!

6.5
 Constant-Pressure Calorimetry

qsys = qwater + qcal + qrxn

qsys = 0
qrxn = - (qwater + qcal)
qwater = m x s x t
qcal = Ccal x t

Reaction at Constant P
H = qrxn

No heat enters or leaves!

6.5
6.5
 Question
• When 0.7521 g of an acid was burned in a calorimeter containing
1,000. g of water, a temperature rise of 3.60°C was observed. What is
the heat capacity of the bomb calorimeter, excluding the water? The
heat of combustion of acid is –26.42 kJ/g. The specific heat of water =
4.18 J/g·°C.

1.34 kJ/°C
 Question
• When 0.7521 g of an acid was burned in a calorimeter containing
1,000. g of water, a temperature rise of 3.60°C was observed. What is
the heat capacity of the bomb calorimeter, excluding the water? The
heat of combustion of acid is –26.42 kJ/g.
 Enthalpy of Formation, ΔHfo
• A formation reaction is a reaction (often hypothetical), in which one
mole of a compound is formed from its constituent elements under
standard conditions (p = 1 atm, T = 298K), and with the elements in
their natural state under standard conditions.

• Examples:
 H2(g) + ½O2(g) → H2O(l)
 2C(s) + 3H2(g) + ½O2(g) → C2H5(OH) (l)
 2Na(s) + S(s) + 2O2(g) → Na2SO4(s)

• The standard enthalpy (heat) of formation is the enthalpy change of

the (hypothetical) formation reaction. Symbol ΔHfo

• Then for a reaction: Reactant → Product:

• ΔHrxno = ΣΔHfo(products) – Σ ΔHfo(reactants)

6.6
 Example
To which one of the following reactions occurring at 25°C does the
symbol H°f[H2SO4(l)] refer ?

•2H(g) + S(g) + 4O(g)  H2SO4(l)

•H2(g) + S(g) + 2O2(g)  H2SO4(l)

•H2SO4(l)  H2(g) + S(s) + 2O2(g)

•H2(g) + S(s) + 2O2(g)  H2SO4(l)

Because there is no way to measure the absolute value of
the enthalpy of a substance, must I measure the enthalpy
change for every reaction of interest?

Establish an arbitrary scale with the standard enthalpy of

formation (H0f ) as a reference point for all enthalpy
expressions.

Standard enthalpy of formation (H0f) is the heat change

that results when one mole of a compound is formed from
its elements at a pressure of 1 atm.

The standard enthalpy of formation of any element in its

most stable form is zero.
H0f (O2) = 0 H0f (C, graphite) = 0
H0f (O3) = 142 kJ/mol H0f (C, diamond) = 1.90 kJ/mol
6.6
6.6
Hess’ Law and enthalpy of reaction calculations
Hess’ Law:

Whether we go from reactant A to product D in one step (A → D), or

whether we go in multiple steps A →B →C →D, the enthalpy change
is the same,

ΔHA →D= ΔHA →B + ΔHB →C + ΔHC →D

When we add, subtract, multiply, or reverse chemical reactions, we can

do the same with the enthalpy change:
For instance if we have
A→B ΔH1
then for 2A→2B ΔH = 2ΔH1
and for B→A ΔH = –ΔH1
P4 (s) + 5O2 (g) P4O10 (s) H = -3013 kJ
etc.
P4O10 (s) P4 (s) + 5O2 (g) H = +3013 kJ
The standard enthalpy of reaction (Hrxn
0
) is the enthalpy of
a reaction carried out at 1 atm.

aA + bB cC + dD

Hrxn
0
= [ cH0f (C) + dH0f (D) ] - [ aH0f (A) + bH0f (B) ]

Hrxn
0
=  nH0f (products) -  mHf0 (reactants)

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.

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

there, only where you start and end.)
6.6
C (graphite) + 1/2O2 (g) CO (g)
CO (g) + 1/2O2 (g) CO2 (g)
C (graphite) + O2 (g) CO2 (g)

6.6
Enthalpy of Formation from Combustion Reactions

• For many hydrocarbons, we measure the enthalpy of combustion, and

then calculate the enthalpy of formation.

C3H8 + 5O2 → 3CO2(g) + 4H2O(l) ΔHcomb = -2.22x103 kJ/mol

Then:
• ΔHcomb = 3ΔHfo(CO2) +4 ΔHfo(H2O(l)) – 5 ΔHfo(O2) – ΔHfo(C3H8)

• We can look up the values for CO2 and H2O(l), and of course O2 = 0:
• -2.22x103 = 3x(-393) + 4x(-286) – 0 – ΔHfo(C3H8)
• And we find:
ΔHfo(C3H8) = -103 kJ/mol
 Benzene (C6H6) burns in air to produce carbon dioxide and
liquid water. How much heat is released per mole of
benzene combusted? The standard enthalpy of formation
of benzene is +49.0 kJ/mol.
2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

Hrxn
0
=  nH0f (products) -  mHf0 (reactants)

Hrxn
0
= [ 12H0f (CO2) + 6H0f (H2O)] - [ 2Hf0 (C6H6) ]

Hrxn
0
= [ 12x–393.5 + 6x–285.6 ] – [ 2x49.0 ] = -6533 kJ

-6533 kJ
= - 3267 kJ/mol C6H6
2 mol

6.6
Ethyl alcohol is produced by the fermentation of glucose, C6H12O6.
C6H12O6(l) → 2 C2H5OH(l) + 2 CO2(g) ΔH° = -82.0 kJ
Given that the enthalpy of formation is -277.7 kJ/mol for C2H5OH(l) and
-393.5 kJ/mol for CO2(g), find the enthalpy of formation for C6H12O6. Is
it exothermic or endothermic?

-1260 kJ/mol
 Group Work
• Exothermic system causes surrounding to _____________
(warm up or cool down)?
• You need 44 kJ of energy to boil one mole of water
(convert from liquid to water vapors). How much heat will
be released to cool down one mole of water vapors to liquid
water?
 Group Work
• Exothermic system causes surrounding to __warm
up___________ (warm up or cool down)?
• You need 44 kJ of energy to boil one mole of water
(convert from liquid to water vapors). How much heat will
be released to cool down one mole of water vapors to liquid
water?
– It will release 44 kJ of energy – Law of conservation of energy.
 Group Work -- TH
Consider following combustion reaction:
2C4H10(g) + 13O2(g)  8CO2(g) + 10H2O(l) H°rxn = –5,314 kJ
How much heat (kJ) will be produced by burning 12.0 g of C 4H10? (MM
of C4H10 is 58.12 g/mol)
 Group Work
Consider following combustion reaction:
2C4H10(g) + 13O2(g)  8CO2(g) + 10H2O(l) H°rxn = –5,314 kJ
How much heat (kJ) will be produced by burning 12.0 g of C 4H10?

–549. kJ
 Example
The combustion of butane produces heat according to the equation
2C4H10(g) + 13O2(g)  8CO2(g) + 10H2O(l) H°rxn= –5,314 kJ/mol
How many grams of CO2 are produced per 1.00 x 104 kJ of heat released?
 Example
The combustion of butane produces heat according to the equation
2C4H10(g) + 13O2(g)  8CO2(g) + 10H2O(l) H°rxn= –5,314 kJ/mol
How many grams of CO2 are produced per 1.00 x 104 kJ of heat released?

662 g
 Group Work
• C3H8 + 5O2 → 3CO2(g) + 4H2O(l) ΔHxn0 = -2.22x103 kJ/mol
• Find ΔHrxn0 for 6CO2(g) + 8H2O(l)  2C3H8 + 10O2
 Example
• C3H8 + 5O2 → 3CO2(g) + 4H2O(l) ΔHxn0 = -2.22x103 kJ/mol
• Find ΔHrxn0 for 6CO2(g) + 8H2O(l)  2C3H8 + 10O2