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Thermochemistry

Chapter 5

Thermochemistry

Thermochemistry:
Relationships between chemical reactions
and energy changes
Thermodynamics:
Therm: heat
Dynamics: power
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Energy
Energy: the capacity to do work

Radiant energy

Thermal energy

Chemical energy

Nuclear energy

Potential energy- relative to position- stored in bonds


electrostatic potential energy (C) = kQ1Q2
d

Kinetic energy Ek = mv2

Units of Energy: J = 1kg-m2/s2 1 cal= 4.184 J

Energy Changes in Chemical Reactions


Which one has more thermal energy?

900C

Coffee cup?

900C

Bathtub?
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Energy Changes in Chemical Reactions


Which one has more thermal energy?

900C

What additional
information is
needed?
400C

How does it relate to heat?

Energy Changes in Chemical Reactions


Heat:
the transfer of _______ between two bodies that are
at ________temperatures.
Temperature is a measure of the ________.
Measure of the ______________
Temperature = Thermal Energy
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Energy Changes
The system is the specific part of the universe that is of
interest in the study.
SYSTEM
SURROUNDINGS

open
Exchange: mass & energy

closed

isolated

energy

nothing

Energy Changes

Enthalpy
Exothermic process: is any process that gives off heat
transfers thermal energy from the system to the surroundings.
2H2 (g) + O2 (g)
H2O (g)

2H2O (l) + energy


H2O (l) + energy

Endothermic process is any process in which heat is supplied


to the system from the surroundings.
energy + 2HgO (s)
energy + H2O (s)

2Hg (l) + O2 (g)


H2O (l)
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Enthalpy
Enthalpy: a thermodynamic quantity used to

describe heat changes(absorbed/released) at


constant pressure (most reactions occur at constant
pressure).

H = E + PV

Equation:
Hreaction = Hproducts - Hreactants
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Enthalpy: Enthalpy Diagrams


H = H (products) H (reactants)
H = heat given off or absorbed during a reaction at constant pressure

Hproducts < Hreactants


H < 0

Hproducts > Hreactants


H > 0

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Enthalpy: Enthalpy Diagrams

Hrxn= Hproducts Hreactants

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Enthalpy: Examples
Indicate the sign of enthalpy change in the
following processes carried under atmospheric
pressure, and indicate whether the process is
exothermic or endothermic:
1.
2.

An ice cube melts


1 g of butane (C4H10) is combusted in sufficient
oxygen to give complete combustion to CO2 and
H2O

3.

A bowling ball is dropped from a height of 8 ft into a


bucket of sand.
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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
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6.3

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
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6.3

Thermochemical Equations: Rules


Stoichiometric coefficients: equal the number of moles
of a substance
H2O (s)

H2O (l)

H = 6.01 kJ

If you reverse a reaction, the sign of H changes


H2O (l)

H2O (s)

H =

- 6.01 kJ

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 = 12.0 kJ
2 x 6.01kJ/mol
=12.0 KJ/2 mol

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Thermochemical Equations: Rules

When a reaction
is reversed, the
magnitude of H
remains the same,
but its sign
changes.

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Thermochemical Equations: Rules


The physical states of all reactants and
products must be specified in thermochemical
equations.
H2O(s) H2O(l)

H = 6.00 kJ

H2O(l)

H = 44.0 kJ

H2O(g)

What will be the H when 1 mole of ice at


0C is changed into one mole of steam at the
boiling point?
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Thermochemical Equations: Rules


How much heat is evolved when 266 g of white
phosphorus (P4) burn in air?
P4 (s) + 5O2 (g)

266 g P4

P4O10 (s)

1 mol P4
123.9 g P4

-3013 kJ
1 mol P4

H = -3013 kJ

[ -6470 kJ]

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Enthalpy: Examples
4. The complete combustion of liquid octane, C8H18, to
produce carbon dioxide and liquid water at 25 C and
at constant pressure gives off 47.9 kJ per gram of
octane. Write a chemical equation to represent this
information.
[2C8H18(l) + 25 O2(g) 16 CO2(g) + 9H2O(l)
H = -1.09 x 104 kJ]

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Enthalpy: Examples
5.

Given the thermochemical equation:


SO2(g) + O2(g) SO3(g) H = -99.1 kCal
Calculate the heat evolved when 74.6 g of SO2
(MM = 64.07 g/mol) is converted to SO3.
[ -115 kJ]

6.

Hydrogen peroxide can decompose to water and oxygen


by the following reaction:
2H2O2(l) 2H2O(l) + O2(g) H = -196 kJ
Calculate the value of q (heat evolved or absorbed) when
5.00 g of H2O(l) decomposes at constant pressure.
[ -14.4 kJ]
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Enthalpy: Examples
7.

Given the equation


H2(g) + I2(s) 2HI(g)

H = +52.96 KJ

Calculate H for the reaction


HI(g) H2(g) + I2(s)
[ -26.48 kJ]

8.

Given the equation:


3O2(g) 2O3(g)
H = +285.4 kJ
Calculate H for the following reaction:
3/2 O2(g) O3(g)
[ 142.7 kJ]
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Calorimetry and Heat Exchanges in a


Chemical Reaction
Read Section 6.4 (Pages 213-2200)
Examples: pp. 216 220: 6.1 6.3
Exercises: pp. 240: 6.19, 6.23, 6.26, 6.28

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Calorimetry
Calorimetry is
performed in
devices called
calorimeters
Calorimetry is
based on the
Law of
Conservation of
Energy

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Calorimetry
9. The specific heat of aluminum is 0.895 J/g C.
Calculate the heat necessary to raise the
temperature of 40.0 g of aluminum from -20.0
C to 32.3 C. Specific heat of aluminum is
0.215-cal/g C.
[1.87 x 103 Joules]

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Calorimetry: Heat Capacity

Calorimetry:
Experimental measurement of heat produced in chemical and
physical processes
Heat Capacity, C, of a system:
the quantity of heat needed to raise the temperature of
matter 1 K.
Units: J/C

q
C
T
Molar Heat Capacity:

The heat required to raise 1 mole of a


substance, 1 K.

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Calorimetry: Specific Heat


Specific heat of a substance
(also represented by cp):
the amount of heat (q) required to raise the temperature of one
gram of the substance by one degree Celsius ( or 1 K).

heat capacity C
Specific heat

mass
m
Specific heat :

q
but C
T

C
q 1
q
cp

( )
m
T m
mT
q mc p T

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Calorimetry: Definitions
Heat (q) absorbed or released:
q = mcpt
q = Ct
t = tfinal - tinitial
When q>0 endothermic reaction
When q<0 exothermic reaction
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Calorimetry: Specific Heat


10.

How much heat, in joules and kilojoules, does it


take to raise the temperature of 225 g of water from
25.0 C to 100.0 C
[ 7.05 x 104 J; 70.5 kJ]

11. Calculate the heat capacity, specific heat and the


molar heat capacity of an aluminum block that has
mass of 5.7 g that must absorb 629 J of heat from
its surroundings for its temperature to rise from 22
C to 145 C.
[C = 5.11 J/C; cp = 0.90 J g-1 C-1, 24 J mol-1 C-1 ]

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Calorimetry: Problems
12. What will be the final temperature if a 5.00-g
silver ring at 37.0 C gives off 25.0 J of heat to
the surroundings? Specific heat of silver = 0.235
J g-1 C-1
[15.7 C]
13. A 15.5 g sample of a metallic alloy is heated to
98.9 C and then dropped into 25.0 g of water in
a calorimeter. The temperature of the water
rises from 22.5 C to 25.7 C. Calculate the
specific heat of the alloy.
[0.29 J g-1 C-1]
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Calorimetry: Problems
14. Suppose a piece of gold with a mass
of 21.5 g at temperature of 95.00 C is
dropped into an insulated calorimeter
containing 125.0 g of water at 22.00 C.
What will be the final temperature of the
water?
[22.4 C]
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Measuring Enthalpy Changes for


Chemical Reactions: ConstantVolume Calorimetry

Bomb Calorimeter

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Constant Volume Calorimeter: Isolated


System
Isolated system:
No exchange of
matter and energy

Uses Cp of water

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Constant-Volume Calorimetry: Isolated system


qsys = qwater + qbomb + qrxn = 0
There is no heat exchange with the surroundings

qrxn = - (qwater + qbomb)


Cbomb= mbombx cbomb
qbomb = Cbombt

qwater = mwcpt

qrxn = -(qwater + Cbombt) = -(mwcpt + Cbombt)


qrxn = - (mwcp + Cbomb)t
Measured heat is not enthalpy:
constant volume

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Constant Volume Calorimetry: Problems


15. In a preliminary experiment, the heat

capacity of a bomb calorimeter assembly is


found to be 5.15 kJ/C. In a second
experiment. A 0.480 g sample of graphite
(carbon) is placed in the bomb with an excess
of oxygen. The water, bomb, and other
contents of the calorimeter are in thermal
equilibrium at 25.00 C. The graphite is
ignited and burned, and the water
temperature rises to 28.05 C. Calculate H
for the reaction.
C(graphite) + O2(g) CO2(g)
[H = -393 kJ]
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Measuring Enthalpy Changes for


Chemical Reactions

Coffee-Cup Calorimeter:
Constant pressure

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Constant-Pressure Calorimetry
qsys = qwater + qcal + qrxn
qsys = 0
qrxn = - (qwater + qcalor)
qwater = mcpt
qcal = Ccalt

Reaction at Constant P
No heat enters or leaves!
Insulated system!
Pressure is constant.

H = qrxn = - (qwater + qcalor)


Measured heat is the
enthalpy

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Calorimetry

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Constant Pressure Calorimetry: Problems


16. (a) A 50.0 mL sample of 0.250 M HCl at 19.50 C is
added to 50.0 mL of 0.250 M NaOH, also at 19.50 C, in
a calorimeter. After mixing, the solution temperature
rises to 21.21 C. Calculate the heat of this reaction.
Assume te volumes of the solutions are additive. Ignore
the heat absorbed by the calorimeter.
[-715 J]
(b) Determine the value of H that should be written in
the equation for the neutralization reaction:
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l) H = ?
[-57.2 kJ]
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Calorimetry: Problem
17. A quantity of 1.00 x 102 mL of 0.500M HCl is
mixed with 1.00 x 102 mL of 0.500 M NaOH in a
constant pressure calorimeter having a heat
capacity of 335 J/ C. The initial temperature of the
HCl and NaOH solutions is the same, 22.50 C, and
the final temperature of the mixed solution is 24.90
C. Calculate the heat change for the neutralization
reaction and the molar heat of the neutralization
reaction. Assume s = 4.18 J/gC for the solution.
[-2.81 kJ; -56.2 kJ/mol]
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Chemistry in Action:
Fuel Values of Foods and Other Substances
C6H12O6 (s) + 6O2 (g)

6CO2 (g) + 6H2O (l) H = -2801 kJ/mol

1 cal = 4.184 J

One food Calorie:


1 Cal = 1000 cal = 4184 J

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Standard Enthalpy of Formation


Absolute value of the enthalpy of a substance cannot be
measured. We need a frame of reference.
Standard states for elements and compounds has to be
established.
Standard state for a solid or liquid substance is the pure
element or compound at 1 atm at a given temperature.
Standard state for gas: pure gas behaving as an ideal
gas at 1 atm and temperature of interest.
Standard enthalpy of formation: the enthalpy change for
a reaction in which the reactants in their standard state
yield products in their standard states. Standard state
denoted with a superscript ()
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Standard Enthalpy of Formation


Standard enthalpy of formation Hf (also called heat of
formation
enthalpy change that occurs in the formation of 1 mole of
the substance from its elements when both products and
reactants are in their standard states (f stands for
formation).
Reference forms:
standard enthalpy of formation of a pure element in its
reference form is 0.
standard enthalpy of formation (H0) as a reference
point for all enthalpy expressions is the formation of H2(g)
= 0 kJ/mol
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Standard Enthalpy of Formation


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 and 25 C .
The standard enthalpy of formation of any element in
its most stable form is zero.
H0f (O2) = 0
H0f (O3) = 142 kJ/mol

H0f (C, graphite) = 0


H0f (C, diamond) = 1.90 kJ/mol

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standard
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Determination of Heat of Formation


1. Direct method: From elements when it can be easily
measured.
C(graphite) + O2(g) CO2(g) Hrxn = -393.5 kJ
Hrxn= HoCO2 H0O2 Hgraphite = -393.5 kJ
H0CO2 = -393.5 kJ

2. Indirect method: Using the heat of reaction and


heats of formations
Given CH4(g) +2O2(g) CO2(g) + 2H2O(g) Hrxn=-890.3 kJ

Calculate the heat of formation of CH4


[-74.8kJ/mol]

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Standard Enthalpy of Reaction


0
The standard enthalpy of reaction (Hrxn
) is the enthalpy of
a reaction carried out at 1 atm and 25C.

aA + bB

cC + dD

H0rxn = [ cH0f (C) + dH0f (D) ] - [ aH0f (A) + bH0f (B) ]


H0rxn = nH0f (products) - mHf0 (reactants)

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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)

H0rxn = nH0f (products) - mHf0 (reactants)


H0rxn = [ 12Hf0 (CO2) + 6Hf0 (H2O)] - [ 2Hf0 (C6H6)]
H0rxn = [ 12x393.5 + 6x187.6 ] [ 2x49.04 ] = -5946 kJ
-5946 kJ
= - 2973 kJ/mol C6H6
2 mol
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Standard Enthalpy of Reaction


18. Synthesis gas is a mixture of carbon monoxide and
hydrogen that is used to synthesize a variety of
organic compounds, such as methanol. One reaction
for producing synthesis gas is shown here:
3CH4(g) + 2H2O(l) + CO2(g) 4CO(g) + 8H2(g)
H = ?
[747.5 kJ]

19. The combustion of isopropyl alcohol, common rubbing


alcohol, is represented by this equation:
2(CH3)2CHOH(l) + 9O2(g) 6CO2(g) + 8H2O(l)
H = -4011 kJ
use this equation and data from Thermodynamic
tables to establish the standard enthalpy of formation
for isopropyl alcohol.
[ -318 kJ/mol]

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Heat of Formation: Examples


20. Pentaborane-9, B5H9, is a colorless liquid. It is highly
reactive substance that will burst into flame or even
explode when exposed to oxygen:
2B5H9(l) + 12O2 5B2O3(s) + 9H2O(l)
It was considered a potential rocket fuel as it release large
amount of heat per gram. Calculate the kJ of heat
released per gram of the compound reacted with oxygen.
The standard enthalpy of formation of B5H9 is 73.2 kJ/mol
[-71.58 kJ/gB5H9]

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Heat of Reactions (Formations):


Hesss Law of Constant heat of Summations

Hesss 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 doesnt matter how you get


there, only where you start and end.)

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Hess Law: Example


Given the following reactions:
CO(g) + O2(g) CO2(g)

H = -283.0 kJ

C(graphite) + O2(g) CO2(g)

H = -393.5 kJ

Calculate the enthalpy for the formation of CO


from its elements
C(graphite) + O2(g) CO(g)
H = ?

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Hesss Law: Example

53

Calculate the standard enthalpy of formation of CS2 (l)


given that:
0
C(graphite) + O2 (g)
CO2 (g) Hrxn
= -393.5 kJ
S(rhombic) + O2 (g)
CS2(l) + 3O2 (g)

SO2 (g)

0
Hrxn
= -296.1 kJ

CO2 (g) + 2SO2 (g)

H0rxn = -1072 kJ

1. Write the enthalpy of formation reaction for CS 2


C(graphite) + 2S(rhombic)

CS2 (l)

2. Add the given rxns so that the result is the desired rxn.
C(graphite) + O2 (g)
2S(rhombic) + 2O2 (g)
+ CO2(g) + 2SO2 (g)
C(graphite) + 2S(rhombic)
6.6

CO2 (g) H0rxn = -393.5 kJ


0
2SO2 (g) Hrxn
= -296.1x2 kJ
CS2 (l) + 3O2 (g)

H0rxn = +1072 kJ

CS2 (l)

H0rxn= -393.5 + 2(-296.1) + 1072 = 86.3 kJ

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Hess Law: Examples


21. Given
C(graphite) + O2 (g) CO2(g)

Hrxn= -393.5 kJ

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


2C2H2(g) + 5O2(g) CO2(g) + 2H2O(l)

Hrxn = -285.8 kJ
Hrxn = -2598.8 kJ

Calculate the heat of formation of C2H2(g)


2C(graphite) + H2(g) C2H2(g)
[52.3 kJ]

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Hess Law: Conceptual Example


Without performing a
calculation, determine
which of the two
substances should
yield the greater
quantity of heat upon
Complete combustion,
on a per mole basis:
ethane, C2H6(g), or
ethanol, CH3CH2OH(l)

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The Solution Process for NaCl

Hsoln = Step 1 + Step 2 = 788kJ 784kJ = 4 kJ/mol

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The enthalpy of solution (Hsoln) is the heat generated or


absorbed when a certain amount of solute dissolves in a
certain amount of solvent.
Hsoln = Hfinal soln - Hcomponents

Which substance(s) could be


used for melting ice?
Which substance(s) could be
used for a cold pack?
Which substances could be
used for hot pack?
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Heat of Solution and Dilution


The process: NaCl(s) Na+(aq) + Cl-(aq)
The steps:
1. Separate ions in the crystal into ions in
gaseous state
2. Hydration of the gaseous ions
Energy involved:
Lattice Energy, U
Hydration energy, H hydration

H solution= U + H hydration

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Heat of Solution and Dilution


Lattice energy: energy required to completely
separate one mole of solid ionic compound into
gaseous ions (endothermic process)
U + NaCl(s) Na+(g) + Cl-(g)

Hydration of the gaseous ions


Heat of hydration: energy released when
ions interact with water molecules.
Na+(g) + Cl-(g) Na+(aq) + Cl-(aq) + Energy

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Heat of Dilution
The heat change associated with the
dilution of a solution.
Can be exothermic or endothermic

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