Energy Changes in Chemical Rxns
Chapter 8
Thermochemistry:
Chemical Energy
Types of Energy
z Work (w): energy transfer when forces are
applied to a system
z Heat (q): energy transferred from a hot object
to a cold one
Radiant energy heat from the sun
Thermal energy associated with motion of
particles
Potential energy energy associated with objects
position or substances chemical bonds
Kinetic energy energy associated with objects
motion
Energy and Energy Conservation
z Heat: form of energy transferred from object at
higher temperature to one at lower temperature
(from hot object to cold object)
z Thermochemistry: study of heat changes in
chemical reactions, in part to predict whether
or not a reaction will occur
z Thermodynamics: study of heat and its
transformations
z First Law of Thermodynamics: Energy can
be converted from one form to another but
cannot be created or destroyed
z Most reactions give off or absorb energy
z Energy is the capacity to do work or supply
heat.
Heat: transfer of thermal (kinetic) energy between
two systems at different temperatures (from hot to
cold)
Metal bar in water Metal bar drilled
Heat versus Temperature
z Describe the difference between the two.
SI unit of energy: J 1 J = 1 kg m
2
z
s2 Molecular heat transfer
z 1 watt = 1 J/s,, so a 100 Watt bulb uses 100 J each
second
z We often use the unit of kJ to refer to chemical heat
exchanges in a reaction. 1 kJ = 1000 J
z Energy is also reported in calories:
Amount of energy needed to raise 1 gram of water by 1oC
1 cal = 4.184 J; 1 Cal = 4184 J
Cal (or kcal) is used on food labels
Conservation of Energy
1
System and Surroundings Endothermic vs Exothermic

z Endothermic reaction: q is positive (q > 0)

Reaction (system) absorbs heat
Surroundings feel cooler
z Exothermic reaction: q is negative (q < 0)
Reaction releases heat
Surroundings feel warmer

z System loses heat (negative); gains heat

(positive)

Applications of heat
emission/absorption Specific Heat and Heat Capacity

z Specific heat (sp. ht.): amount of heat

required to raise 1 gram of substance by 1oC
z Use mass, specific heat, and T to calculate
the amount of heat gained or lost:
z q = msT ms = C q = CT
Heat capacity (C): amount of heat required to raise
the temperature of a given quantity of a substance
by 1oC; C = q / T = J / oC
Molar heat capacity (Cm): amount of heat that can
be absorbed by 1 mole of material when
temperature increases 1oC; q = (Cm) x (moles of
substance) x (T) = J / mol oC
9

Specific Heat and Heat Capacity Practice Problem

z Calculate the amount of heat transferred when 250 g of

H2O (with a specific heat of 4.184 J/goC) is heated
from 22oC to 98oC.
z q = msT
z Is heat being put into the system or given off by the
system?

z If a piece of hot metal is placed in cold water, what

gains heat and what loses heat? Which one will have
a positive q value and which will have a negative q
value?
z Worked Ex. 8.4, 8.5; Problems 8.10 8.12

2
Practice Problem Calorimetry and Heat Capacity

z 34.8 g of an unknown metal at 25.2oC is mixed z Heat changes in a reaction

with 60.1 g of H2O at 96.2 oC (sp. ht. = 4.184 can be determined by
J/goC). The final temperature of the system measuring the heat flow at
comes
co es to
o 88
88.4oC
C. Identify
de y the euunknown
o metal.
ea constant
co sa p pressure
essu e
z Apparatus to do this is
z Specific heats of metals: called a calorimeter.
Al 0.897 J/goC z Heat evolved by a reaction
Fe 0.449 J/goC is absorbed by water; heat
Cu 0.386 J/goC capacity of calorimeter is
Sn 0.228J/goC the heat capacity of water.
13 14

Example Enthalpies of Physical/Chemical Changes

z A 28.2 gram sample of nickel is heated to z Enthalpy (H) describes heat flow into and out
99.8oC and placed in a coffee cup calorimeter of a system under constant pressure
containing 150.0 grams of water at 23.5oC.
After the metal cools, the final temperature of z Enthalpy (a measure of energy) is heat
th metal
the t l andd water
t iis 25
25.0
0oC.
C transferred per mole of substance
substance.
z qabsorbed + qreleased = 0 z At constant pressure,
z Which substance absorbed heat? qp = H = Hproducts Hreactants

z Which substance released heat? H > 0 endothermic (net absorption of energy

from environment; products have more internal
z Calculate the heat absorbed by the substance energy)
you indicated above.
H < 0 exothermic (net loss of energy to
environment; reactants have more internal energy)

Heating a Pure Substance (Water) Enthalpies of Phase Changes

z Why does T become
constant during
melting and
evaporating?
z M lti
Melting, vaporization,
i ti
and sublimation are
endothermic
z We can calculate
2.09 J/g
total heat needed to
convert a 15 gram
piece of ice at -20oC
to steam at 120oC.
2.080 J/goC z Heat of fusion (Hfus): Amount of heat required
to melt (solid liquid)
2250 J/g
z Heat of vaporization (Hvap): Amount of heat
4.184 J/goC
required to evaporate (liquid gas)
334 J/g
z Heat of sublimation (Hsub): Amount of heat
required to sublime (solid gas)
J/goC
z Why are there no values for Hfreezing,
Hcondendsation, or Hdeposition?
17

3
Enthalpies of Reaction Thermochemical Equations

z Determine if the following processes are z Shows both mass and enthalpy relationships
endothermic or exothermic z 2Al (s) + Fe2O3 (s) 2Fe (s) + Al2O3 (s)
Combustion of methane Ho = -852 kJ
Reacting Ba(OH)2 with NH4Cl z Amount of heat given off depends on amount
Neutralization of HCl of material:
Melting 852 kJ of heat are released for every 2 mol Al, 1 mol
CaCO3 (s) CaO (s) + CO2 (g) Fe2O3, 2 mol Fe, and 1 mol Al2O3

19

Thermochemical Equations Hesss Law

z 2Al (s) + Fe2O3 (s) 2Fe (s) + Al2O3 (s) Ho = - z If a compound cannot be directly synthesized
852 kJ from its elements, we can add the enthalpies of
z How much heat is released if 10.0 grams of Fe2O3 multiple reactions to calculate the enthalpy of
reacts with excess Al?
reaction
eac o in ques
question.
o
z Worked Ex. 8.3; Problems 8.8, 8.9
z Hesss Law: change in enthalpy is the same
whether the reaction occurs in one step or in a
z What if we reversed the reaction?
series of steps
z Heat would have to be put in to make the reaction
proceed: z Look at direction of reaction and amount of
2Fe (s) + Al2O3 (s) 2Al (s) + Fe2O3 (s) Ho = +852 kJ reactants/products

Hesss Law Hesss Law

z Value changes sign with direction z Values of enthalpy change

For a reaction in the reverse direction, enthalpy is
numerically equal but opposite in sign
z Reverse direction, heat flow changes; endothermic
becomes exothermic (and vice versa); sign of H changes
Proportional to the amount of reactant consumed
z Twice as many moles = twice as much heat; half as many
moles = half as much heat
z HT = H1 + H2 + H3 + .

Figure 8.5
23 24

4
Enthalpy of Chemical Reaction Hesss Law

z Thermochemical equation: z Calculate Ho for

H2(g) + I2(s) 2HI(g) H = +53.00 kJ z 2NO (g) + O2 (g) N2O4 (g) Ho = ?
z Two possible changes:
z Reverse the equation: z N2O4 (g)
( ) 2NO2 (g)
( ) H
Ho = 57.2
2 kJ
2HI(g) H2(g) + I2(s) H = -53.00 kJ z NO (g) + O2 (g) NO2 (g) Ho = -57.0 kJ
z Double the amount of material:
2H2(g) + 2I2(s) 4HI(g) H = +106.00 kJ

25

Hesss Law Hesss Law

z We can use known values of Ho to calculate

unknown values for other reactions
z P4 (s) + 3 O2 (g) P4O6 (s) H = -1640.1 kJ
z P4 (s) + 5 O2 (g) P4O10 (s) H = -2940.1
2940 1 kJ

z What is Ho for the following reaction?

P4O6 (s) + 2 O2 (g) P4O10 (s) H = ?

z Worked Ex. 8.6, 8.7; Problem 8.13, 8.15

27

Hesss Law Standard Heats of Formation

z Given: z Standard heat of formation (Hof): heat
z 2NH3(g) N2H4(l) + H2(g) H = 54 kJ needed to make 1 mole of a substance from its
stable elements in their standard states
z
1
N (g) + 32 H2(g) NH3(g) H = -69 kJ
2 2
z Hof = 0 for a stable (naturally occurring)
z CH4O(l)( ) CH2O(g)(g) + H2(g) H = -195 kJ
element
z Which of these have Hof = 0?
z Find the enthalpy for the following reaction:
CO(g), Cu(s), Br2(l), Cl(g), O2(g), O3(g), O2(s), P4(s)
z N2H4(l) + CH4O(l) CH2O (g) + N2(g) + 3H2(g)
z Do the following equations represent standard
H = ? kJ
enthalpies of formation? Why or why not?
2Ag (l) + Cl2 (g) 2AgCl (s)
Ca (s) + F2 (g) CaF2 (s)
30

5
Standard Enthalpies of Formation Standard Enthalpies of Formation

z Can use measured enthalpies of formation to z Table 8.2: Some Common Substances (25oC)
determine the enthalpy of a reaction (use
Appendix B in back of book)
z Horxn = nHof (products) nHof (reactants)
= sum; n = number of moles (coefficients)
z Direct calculation of enthalpy of reaction if the
reactants are all in elemental form
Sr (s) + Cl2 (g) SrCl2 (g)
Horxn = [Hof (SrCl2)] [Hof (Sr) + Hof (Cl2)]
= -828.4 kJ/mol

Heats of Formation Bond Dissociation Energies

z Horxn = Hof,products - Hof,reactants
z Calculate values of Ho for the following rxns:
z 1) CaCO3 (s) CaO (s) + CO2 (g)
z 2)) 2C6H6 ((l)) + 15O2 (g) 12CO2 (g) + 6H2O ((l))
z Bond Dissociation Energy (or Bond Energy,
BE): energy required to break a bond in 1 mole
of a gaseous molecule
z Reactions generally proceed to form H Bond Energy
2

compounds with more stable (stronger) bonds

z Hof values: (greater bond energy)
CaCO3: -1207.1 kJ/mol; CaO: -635.5 kJ/mol; CO2: -
393.5 kJ/mol; C6H6: 49.0 kJ/mol; H2O(l): -285.8
kJ/mol
z Worked Ex. 8.8, 8.9; Problems 8.16, 8.17

33 34

Bond Dissociation Energies Bond Dissociation Energies

z Bond energies vary somewhat from one mole-

cule to another so we use average bond
dissociation energy (D)
z H-OH 502 kJ/mol Avg O-H = 453
z H-O 427 kJ/mol kJ/mol
z H-OOH 431 kJ/mol

35 36

6
Bond Dissociation Energies Heats of Reaction
z Horxn = BE (reactants) + - BE (products) z Use bond energies to calculate the enthalpy
endothermic exothermic change for the following reaction:
energy input energy released
N2(g) + 3H2(g) 2NH3(g)
z BE(react) > BE(prod) endothermic z Hrxn = [BEN N + 3BEH-H] + [[-6BE
6BEN-H]
z BE(react) < BE(prod) exothermic z Hrxn = [945 + 3(436)] [6(390)] = -87 kJ
z measured value = -92.2 kJ
z Use only when heats of formation are not z Why are the calculated and measured values
available, since bond energies are average different?
values for gaseous molecules

37 38

Heats of Reaction Thermochemistry Calculation Summary

z Use bond energies to calculate the enthalpy z Use q = msT (s = J/goC)

change for the decomposition of nitrogen z If given mass of reactant, convert to moles and
trichloride: multiply by enthalpy to find total heat
NCl
C 3 (g) N2 (g) + C
Cl2 (g) transferred
z How many distinct bond types are there in z If given multiple equations with enthalpies, use
each molecule? Hesss Law
z If given Hof values: products reactants
z How many of each bond type do we need to
calculate Hrxn? z If given bond energy (BE) values: +reactants +
-products
BE(N-Cl) = 200 kJ/mol
BE(NN) = 945 kJ/mol
BE(Cl-Cl) = 243 kJ/mol 39

Practice Problems Practice Problems

z Identify how to set up the following problems: z C2H4(g ) + 6F2(g) 2CF4(g) + 4HF(g) Ho = ?
H2 (g) + F2 (g) 2HF (g) Ho = -537 kJ
z Calculate the Ho of reaction for:
C (s) + 2F2 (g) CF4 (g) Ho = -680 kJ
C3H8 (g) + 5O2 (g) 3CO2 (g) + 4H2O (l)
2C (s) + 2H2 (g) C2H4 (g) Ho = 52.3 kJ
HoC3H8(g): -103.95
103 95 kJ/mol;Ho f CO2(g): -393.5
393 5
f
kJ/mol; Hof H2O(l): -285.8 kJ/mol
z Use average bond energies to determine the
z 8750 J of heat are applied to a 170 g sample of metal,
enthalpy of the following reaction (from Table
causing a 56oC increase in its temperature. What is 7.1).
the specific heat of the metal? Which metal is it? CH4 (g) + Cl2 (g) CH3Cl (g) + HCl (g)
(BEC-Cl = 328 kJ/mol)