Thermochemistry

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Chapter Goals

Heat Changes and Thermochemistry

1. The First Law of Thermodynamics
2. Some Thermodynamic Terms
3. Enthalpy Changes
4. Calorimetry
5. Themochemical Equations
6. Standard States and Standard Enthalpy
Changes
7. Standard Molar Enthalpies of Formation,
DHfo
 Chapter Goals
3

8. Hess’s Law
9. Changes in Internal Energy, DE
Energy

 Capacity to do work
 Units of energy:
. Joule; Kjoule (kJ)
. Calorie
. BTU (British Thermal Unit)

. Pressure-volume units (L-atm, etc)

Forms of Energy
• 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
• Electrical energy is the energy associated with
the flow of electrons
• 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

900C
400C
greater thermal energy
6.2
8 The First Law of
Thermodynamics

 Thermodynamics is the study of the

changes in energy and transfers of
energy that accompany chemical and
physical processes.
The First Law of Thermodynamics
9

 Exothermic
reactions
generate specific
amounts of heat.
 This is because
the potential
energies of the
products are
lower than the
potential energies
of the reactants.
10 The First Law of
Thermodynamics
 This law can be stated as, “The combined amount of
energy in the universe is constant.”
 The first law is also known as the Law of Conservation
of Energy.
 Energy is neither created nor destroyed in chemical
reactions and physical changes.
11 Some Thermodynamic Terms

 The substances involved in the

chemical and physical changes
under investigation are called the
system.
 In chemistry lab, the system is the
chemicals inside the beaker.
 The environment around the system is
called the surroundings.
 The surroundings are outside the beaker.
 The system plus the surroundings is
called the universe.
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
13 Changes in Internal Energy,
DE
 The internal energy, E, is all of the energy contained
within a substance.
 This function includes all forms of energy such as kinetic,
potential, gravitational, electromagnetic, etc.
 The First Law of Thermodynamics states that the change
in internal energy, DE, is determined by the heat flow, q,
and the work, w.
 Changes in Internal Energy,
DE
DEDEEE=
D products  E
 E reactants
EEproducts
products E reactants
reactants
D
DEDEEq= qwq w+ w
q  0 if heat is absorbed by the system.
q  0 if heat is absorbed by the system.
q  0 if heat is absorbed by the system.
wq 0 if0 the
if heat is absorbed
surroundin byonthe
gs do work the system.
system.
w  0 if the system does work on the surroundin gs.
 Thermodynamics
DE = q + w
DE 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 = -PDV when a gas expands against a constant external pressure

6.7
Changes
16 in Internal Energy, DE

 DE is negative when energy is released by a

system undergoing a chemical or physical
change.
 Energy can be written as a product of the process.

C 5 H 12 (  )  8 O 2(g)  5 CO 2(g)  6 H 2 O (  )  3.516  10 3 kJ

D E  - 3.516  10 3 kJ
Changes
17 in Internal Energy, DE

 DE is positive when energy is absorbed by a

system undergoing a chemical or physical
change.
 Energy can be written as a reactant of the process.

5 CO 2(g)  6 H 2 O (  )  3.516  10 kJ  C 5 H 12 (  )  8 O 2(g)

3

D E   3.516  10 3 kJ
Changes in Internal Energy, DE

 Example 15-12: If 1200 joules of heat are added

to a system in energy state E1, and the system
does 800 joules of work on the surroundings,
what is the :
1. energy change for the system, DEsys

DE = E 2 - E1 = q + w
DE = 1200 J + (-800 J)
DE = 400 J
DE sys = + 400 J
Changes
19 in Internal Energy, DE

2. energy change of the surroundings, DEsurr

You do it!

DE surr  400 J
 Changes in Internal Energy,
DE
3. energy of the system in the new state, E2

DE sys  E 2 - E1
E 2  E1  DE sys
 E1  400 J
 The First Law of
Thermodynamics
 Exothermic reactions release energy in the form of heat.
 For example, the combustion of propane is exothermic.

C 3 H 8 (g )  5 O 2 (g )  3 C O 2 (g )  4H 2 O (  )  2.22  10 3 kJ
 The combustion of n-butane is also exothermic.

2 C 4 H 1 0 (g )  13 O 2 (g )  8 C O 2 (g )  10 H 2 O (  )  5.78  10 3 kJ
Enthalpy (H) is used to quantify the heat flow into or out of a
system in a process that occurs at constant pressure.
DH = H (products) – H (reactants)
DH = heat given off or absorbed during a reaction at constant pressure

Hproducts < Hreactants Hproducts > Hreactants

DH < 0 DH > 0 6.3
 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

Is DH negative or positive?

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
 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
 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
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 = ms

Heat (q) absorbed or released:

q = msDt
q = CDt
Dt = tfinal - tinitial

6.4
 How much heat is given off when an 869 g iron bar cools
from 940C to 50C?

s of Fe = 0.444 J/g • 0C

Dt = tfinal – tinitial = 50C – 940C = -890C

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

6.4
 Constant-Volume Calorimetry

qsys = qwater + qbomb + qrxn

qsys = 0
qrxn = - (qwater + qbomb)
qwater = msDt
qbomb = CbombDt

Reaction at Constant V
DH = qrxn
DH ~ qrxn
No heat enters or leaves!
6.4
 Constant-Pressure Calorimetry –
A coffee-cup calorimeter
is used to measure the amount of heat produced
(or absorbed)
in a reaction at constant P
qsys = qmix + qcal + qrxn
qsys = 0
qrxn = - (qmix + qcal)
qmix = msDt
qcal = CcalDt

Reaction at Constant P
DH = qrxn

No heat enters or leaves!

6.4
Calorimetry

 Example 15-1: When 3.425 kJ of heat is added to a

calorimeter containing 50.00 g of water the
temperature rises from 24.00oC to 36.54oC. Calculate
the heat capacity of the calorimeter in J/oC. The
specific heat of water is 4.184 J/g oC.
 This is a four part calculation.
 Calorimetry

1. Find the temperature change.

DT =  36.54 - 24.00  C = 12.54 C 0 0

2. Find the heat absorbed by the water in going from 24.000C to

36.540C.

q P  mCDT
. 
= 50.00 g 4184 J
0
g C 12.54 C
0

 262337
. J  2623 J
 33 Calorimetry

3. Find the heat absorbed by the calorimeter.

 Take the total amount of heat added to calorimeter and subtract the
heat absorbed by the water.

3.425 kJ = 3425 J
3425 J - 2623 J  = 802 J
4. Find the heat capacity of the calorimeter.
 (heat absorbed by the calorimeter)/(temperature change)

802 J
0
 63.955 J 0  64.00
C
J 0
C
12.54 C
34 Calorimetry

 Example 15-2: A coffee-cup calorimeter is used to

determine the heat of reaction for the acid-base
neutralization

CH3COOH(aq) + NaOH(aq) 
NaCH3COO(aq) + H2O()
When we add 25.00 mL of 0.500 M NaOH at 23.000oC
to 25.00 mL of 0.600 M CH3COOH already in the
calorimeter at the same temperature, the resulting
temperature is observed to be 25.947oC.
35 Calorimetry

The heat capacity of the calorimeter has previously been determined to

be 27.8 J/0C. Assume that the specific heat of the mixture is the same as
that of water, 4.18 J/g0C and that the density of the mixture is 1.02 g/mL.
Calorimetry
36

 This is a three part calculation.

1. Calculate the amount of heat given off in the reaction.

temperature
temperature
temperature change
change
change
D T = 
D T =  25.947 - 23.000
25.947 - 00  0 C = 2.947
23.000 C
23.000 00 0
2.947 CC C
C == 2.947
heatabsorbed
heat absorbed
byby calorimeter
calorimeter
q =
q = 2.947
2.9470 C 27.8
0
J0
J

C 27.8 C   819
 819
0
. JC
. J
mass of solution in calorimeter
102
. g
 25.00 mL + 25.00 mL   510. g
mL
37 Calorimetry

heat absorbed by solution

q = mCDT


q = 51.0 g  418
. J
g0 C  
2.947 0 C  628 J
total amount of heat produced by reaction
q = 81.9 J + 628 J = 709.9 J
Calorimetry
38

2. Determine DH for the reaction under the conditions

of the experiment.
We must determine the number of moles of reactants
consumed which requires a limiting reactant calculation.

 aqaq  NaCH
CH 3COOH
CH 3COOH  + NaOH  NaCH 3COO  aq  + H O l  H 2 O
 aq  +  aq
NaOH 3COO aq2 + l 
 0.500 mmol NaOH 
25.00 mL NaOH 0.500 mmol NaOH
mL NaOH   1 mL NaOH  

25.00  

1 mL NaOH
 1 mmol NaCH 3COO   12.5 mmol NaCH COO
 
 1 
mmol NaCH
1 mmol COO
NaOH   3
 3
  12.5 mmol NaCH 3COO
 1 mmol NaOH   0.600 mmol CH 3COOH 
 25.00 mL CH COOH  
3
 1 mL CH 3COOH 
 1 mmol NaCH 3COO 
   15.0 mmol NaCH 3COO
 1 mmol CH 3COOH 
Calorimetry
39

3. Finally, calculate the DHrxn based on the limiting

reactant calculation.
12.5 mmol = 0.0125 mol
709.9 J
DH rxn   56792 J / mol  56.8 kJ / mol
0.0125 mol
6.4
 Standard States and Standard Enthalpy
Changes
 Thermochemical standard state conditions
 The thermochemical standard T = 298.15 K.
 The thermochemical standard P = 1.0000 atm.
 Be careful not to confuse these values with STP.

 Thermochemical standard states of matter

 For pure substances in their liquid or solid phase the standard
state is the pure liquid or solid.
 For gases the standard state is the gas at 1.00 atm of pressure.
 For gaseous mixtures the partial pressure must be 1.00 atm.
 For aqueous solutions the standard state is 1.00 M
concentration.
 Standard Molar Enthalpies of Formation,
DHfo
 The standard molar enthalpy of formation is defined as
the enthalpy for the reaction in which one mole of a
substance is formed from its constituent elements.
 The symbol for standard molar enthalpy of formation is DHfo.
 The standard molar enthalpy of formation for MgCl2 is:

Mg  s   Cl 2 g   MgCl 2 s   6418
. kJ
DH f MgCl 2  s 
o
 6418
. kJ / mol
 Standard Molar Enthalpies of Formation,
DHfo
 Standard molar enthalpies of formation have been
determined for many substances and are tabulated
in Table 15-1 and Appendix K in the text.
 Standard molar enthalpies of elements in their most
stable forms at 298.15 K and 1.000 atm are zero.
 Example 15-4: The standard molar enthalpy of formation for
phosphoric acid is -1281 kJ/mol. Write the equation for the
reaction for whichDHorxn = -1281 kJ.
P in standard state is P4
Phosphoric acid in standard state is H3PO4(s)
You do it!
 Standard Molar Enthalpies of Formation,
DHfo

3
2 H2g  2 O2g  14 P4s  H3PO4s  1281 kJ
DHf H3PO4 s 
o
 1281 kJ / mol
45
Standard Molar Enthalpies of Formation,
DHfo
Example 15-5: Calculate the enthalpy
change for the reaction of one mole of H2(g)
with one mole of F2(g) to form two moles of
HF(g) at 25oC and one atmosphere.
H 2 g  F2  g   2 H F g 
std. state std. state std. state
for this rxn. D H o298  2 D H of
from A ppendix K , D H of   271 kJ / m ol
D H o298   2 m ol   271 kJ / m ol    542 kJ
 0 ) is the enthalpy of
The standard enthalpy of reaction (DHrxn
a reaction carried out at 1 atm.

aA + bB cC + dD

DH0rxn = [ cDH0f (C) + dDH0f (D) ] - [ aDH0f (A) + bDH0f (B) ]

DH0rxn = S nDH0f (products) - S mDHf0 (reactants)

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 49.04 kJ/mol.

2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

DH0rxn = S nDH0f (products) - S mDHf0 (reactants)

DH0rxn = [ 12DH0f (CO2) + 6DH0f (H2O)] - [ 2DH0f (C6H6)]

DH0rxn = [ 12x–393.5 + 6x–285.8 ] – [ 2x49.04 ] = -6,534.88 k

-6534.88 kJ
= - 3267.44 kJ/mol C6H6
2 mol

6.5
 Hess’s Law
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.)
 Calculate the standard enthalpy of formation of CS2 (l)
given that:
C(graphite) + O2 (g) CO2 (g) DH0rxn = -393.5 kJ
S(rhombic) + O2 (g) SO2 (g) DH0rxn = -296.1 kJ
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) DHrxn
0 = -1072 kJ

1. Write the enthalpy of formation reaction for CS2

C(graphite) + 2S(rhombic) CS2 (l)

2. Add the given rxns so that the result is the desired rxn.
C(graphite) + O2 (g) CO2 (g) DH0rxn = -393.5 kJ
2S(rhombic) + 2O2 (g) 2SO2 (g) DH0rxn = -296.1x2 kJ
+ CO2(g) + 2SO2 (g) CS2 (l) + 3O2 (g) DHrxn
0 = +1072 kJ

C(graphite) + 2S(rhombic) CS2 (l)

6.5 DH 0 = -393.5 + (2x-296.1) + 1072 = 86.3 kJ
rxn
52 Hess’s Law

 Example 15-7: Given the following equations and

DHo values
DH o
 kJ 
[1] 2 N 2 g   O 2 g   2 N 2 O  g  164.1
[2] N 2 g  + O 2 g   2 NO  g  180.5
calculate DHo for the reaction below.
[3] N 2 g  + 2 O 2 g   2 NO 2  g  66.4

N 2 O  g  + NO 2  g   3 NO  g  DH o  ?
You do it!
Hess’s
53 Law

Use a little algebra and Hess’s Law to get

the appropriate DHo values
DHDoH(kJ)
o
D H o
(kJ) (kJ)
1112NN22OOg1g
11 
22 ON22ggg
N2N ++1N1 O + 1 O-82.05
 2 2 gO
2g2g 2 2 g-82.05
 - 82.05
3  2 3 3  N 
2   2 2 2g 2 22g  2g 2 32NO g 
2 3 N3 + 3 O 3 NO  g  270.75
+ O g 270.75
2 
1   3 NO
 2 g   1 N
2 2 g  + O 2 g  - 33.2
N 2 O  g   NO 2 g   3 NO  g  155.5
 Hess’s
54 Law

The + sign of the DHo value tells us that the

reaction is endothermic.
The reverse reaction is exothermic, i.e.,

3 NO  g   N 2 O  g  + NO 2  g  DH o
= - 155.5 kJ
 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