THERMOCHEMISTRY  System

- the portion of the universe selected for a

Thermochemistry thermodynamic study.
 a branch of thermodynamics which concerns with the
measurement, analysis & interpretation of heat that  Surroundings
is involved in physical & chemical reactions. - any part of the universe outside the system.

 Energy
- ability to do work or to transfer heat. surroundings
system
- unit is Joule (J)
1 J = 1 kg-m2/s2
1 calorie = 4.184 J boundary

 Work, W Types of Systems:

- the movement of an object against some force. type example
- directed energy change resulting from a process. can exchange mass &
- 1 L-atm = 101.32 J energy with its glass w/ water,
open
Consider a cylinder with a movable piston, surroundings tree

-P V
W = -P can exchange only
* compression of gas energy with its
closed thermometer
force surroundings but not
mass
cannot exchange
mass & energy with
isolated styrofor ice box
gas h its surroundings

Vi Vf Sign Convention for Heat & Work:

Vi > Vf
ΔV = Vf – Vi = (-) negative W (+)
W = -PΔV = (+) positive
*If work done on the system, W is positive
system
* expansion of gas
q (+) syste q (-)
m
h
W (-)
force gas
Endothermic process
- a process at which heat is absorbed or enters the system
Vi Vf
Vi < Vf Exothermic process
ΔV = Vf – Vi = (+) positive - a process at which heat is released or exits the system
W = -PΔV = (-) negative
*If work done by the system, W is negative  Internal Energy, E
- the total energy possessed by a system
 Heat, q - the change in internal energy, E can be also
-the flow of energy from a body at higher defined as: E = q + w.
temperature to one at a lower temperature when  Enthalpy, H
they are placed in thermal contact. - a quantity defined as the sum of internal energy, E
and PV. (H = E + PV)

note:

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 - enthalpy (as well as internal energy) cannot be
measured directly, but it is actually the change in  Isothermal Process (temperature is constant)
enthalpy, H which can be measured. E = q + w
 H =  E + P
P V E = 0 (for constant temp. process)
0=q+w
for processes involving solids and liquids: q = -w
H = E
- since the volumes of solids & liquids does not change  Adiabatic Process (no heat enters or leaves the
significantly in the process system)
E = q + w
for process involving gases: q = 0 for adiabatic process
using ideal gas equation, PV = nRT E = w
PV = nRT
 H =  E +  nRT Exercises:
 where n = # moles of gaseous products - # moles of A. Determine whether the following are open, closed or
gaseous reactants. isolated system
1. “coleman” water jug
2. pressure cooker in use
 State & Path Functions 3. burning wood
4. rice cooker in use
 State Functions 5. flat iron
- are properties that are determined by the state of the 6. student inside a classroom
system, regardless of how that condition was
achieved. B. For the following processes, calculate the change in
- the change in the magnitude of the state function internal energy of the system & determine whether
depends only on the initial & final states of the the process is endothermic or exothermic:
system & not on how the change is accomplished. 1. A balloon is heated by adding 670 J of heat. It
- examples are energy, pressure, volume, temperature expands, doing 332 J of work on the atmosphere.
& enthalpy 20C to 10
2. A 10.0 g sample of water is cooled from 20 10C
thereby losing approximately 420 J of heat.
 Path Functions 3. A chemical reaction releases 8.65 kJ of heat & does
- properties that are determined via how the conditions no work on the surroundings
are achieved
- examples are work & heat C. The ΔE of the system is –45 J. If 105 J of heat is
being released, calculate w. Is the work done on or
Thermodynamics done by the system.
 the study of energy and its transformations.
Calorimetry
First Law of Thermodynamics - the measurement of heat flow or heat changes as a
 energy can be transformed from one form to result of a chemical reaction.
another, but cannot be created or destroyed - the apparatus used to measure heat flow is called
 energy in the universe is constant calorimeter.

qsys + qsurr = 0 Types of Calorimeter:

 qsys = -qsurr 1. Bomb Calorimeter- a device used to measure the
 Isometric/Isochoric Process (volume is constant) heat of combustion. A bomb calorimeter is
E = q + w considered a constant volume system.
-PV
W = -P 2. Open-type Calorimeter- a device used to determine
V = 0 (since no change in volume) heat changes for non-combustion reactions (e.g. heat
W = 0 of solution, heat of neutralization, heat of dilution)
E = q - an open-type calorimeter is considered as a
constant pressure system
 Isobaric Process (pressure is constant)
E = q + w
-PV
W = -P
E = q + (-P
(-PV)
E + PPV = q
Specific Heat & Heat Capacity
recall: E + P
PV = H
H = q
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Specific Heat, S the calorimeter assembly is 4.90 kJ/ oC. What is the
- amount of heat required to raise the temperature of heat of combustion of sucrose?
on gram of a substance by one degree Celcius. 3. A 1.567 gram sample of naphthalene, C 10H8(s), is
J/gC
- unit is J/g completely burned in a bomb calorimeter assembly
J/gC
- the specific heat capacity of water is 4.184 J/g and a temperature increase of 8.37 oC is noted. When
- if the amount of substance is one mole, it is called a 1.227-gram sample of thymol, C10H14O(s), is burned
molar heat capacity in the same calorimeter assembly, the temperature
increase is 6.12oC. If the heat of combustion of
Heat Capacity, C naphthalene is –5153.9 kJ/mole C 10H8, what is the
- the amount of heat required to raise the temperature heat of combustion of thymol?
of a given quantity of a substance by one degree
Celcius. Constant Pressure Calorimetry
J/C
- unit is J/ - the most common device used is the “coffee-cup”
calorimeter
qsys = qrxn + qmix + qcal
Measuring Heat Change qsys = 0 (since adiabatic)
0 = qrxn + qmix + qcal
C = mS where:
q = mS mSt qmix is the heat of the mixture
q = C C t qrxn can be qneut, qdil, qsoln, etc..
where t = tfinal – tinitial (change in temeperature)
qmix = mmixSmixt
Exercises: qcal = Ccalt
1. A piece of silver of mass 362 g has a heat capacity of qrxn = -qmix –qcal
J/C. What is the specific heat of silver.
85.7 J/ qrxn = - mmixSmix t - Ccal t
2. A 6.22 kg piece of Cu metal is heated from 20.5 C to
324.3 C. Calculate the heat absorbed by the metal. Exercises:
J/gC)
(SCu = 0.385 J/g 1. A quantity of 100 mL of 0.500 M HCl is mixed with
3. Calculate the amount of heat liberated (in kJ) from 100 mL of 0.500 M NaOH in a constant pressure
366 g of mercury when it cools from 77.0 C to 12.0 calorimeter that has a heat capacity of 335 J/ J/C. The
C. (SHg = 0.140 J/g-K) initial temperature of the HCl and NaOH solution is
the same, 22.50 C, and the final temperature of the
Constant Volume Calorimetry mixed solution is 24.90 C. Calculate the heat
- the device used is the bomb calorimeter change for the neutralization reaction:
NaOH(aq) + HCl(aq)  NaCl(aq) + H2O(l)
qsys = qwater + qbomb + qrxn Assume that the densities and specific heats of the
but qcal = qwater + qbomb solutions are the same as for water (1.00 g/mL &
qsys = qcal + qrxn J/gC, respectively).
4.184 J/g
qsys = 0 (since adiabatic) 2. When 50.0 mL of 0.100 M AgNO 3 and 50.0 mL of
0 = qcal + qrxn 0.100 M HCl are mixed in a constant pressure
qrxn = -qcal calorimeter that has a heat capacity of 405 J/ J/C. The
temperature of the mixture increases from 22.30 22.30C to
qcal = Ccal t 23.11C. The temperature increase is caused by this
23.11
where: reaction:
Ccal – heat capacity of calorimeter AgNO3(aq) + HCl(aq)  AgCl(s) + HNO3(aq)
t – change in temperature Calculate H for this reaction, assuming that the
combined solution has a mass of 100.0 g and a
Exercises: specific heat capacity of 4.184 J/gJ/gC.
1. A quantity of 1.922 g of methanol (CH 3OH) was
burned in a constant volume bomb calorimeter.
Consequently, the temperature of the H2O rose by Thermochemical Equations
4.20C. If the quantity of H 2O surrounding the
4.20 - a balanced chemical equation that shows the
calorimeter was exactly 2000.0 g and the heat associated enthalpy change.
kJ/C, calculate
capacity of the calorimeter was 2.02 kJ/ ex:
the molar heat of combustion of methanol. 2H2(g) + O2(g)  2H2O(g) H = -483.6 kJ
2. The combustion of 1.01 grams of sucrose, C 12H22O11,
in a bomb calorimeter causes the water temperature
to rise from 24.92 to 28.33 oC. The heat capacity of
Enthalpy of Formation (or heat of formation),  Hf
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 - energy released or absorbed when 1 mole of a  Hess’s Law (Indirect Method)
compound is formed from its elements. - if a reaction is carried out in a series of steps, H for
ex: the reaction will be equal to the sum of the enthalpy
N2(g) + 6H2(g)  2NH3(g) Hf = -46.19 kJ changes for the individual steps.

Enthalpy of Reaction (or heat of reaction),  Hr
- energy released or absorbed as a result of a certain
reaction
Hr = Hf products - Hf reactants
Standard State of A Substance
- pure form of a substance at atmospheric pressure (1
atm) and temperature of 25 C.
Standard Enthalpy of Reaction,  Hr
- is the enthalpy change when all reactants & products
are in their standard states. The superscript 
indicates standard state conditions.
Guidelines in Using Thermochemical Equations:
1. Enthalpy is an extensive property
- H is dependent on the amount of reactant
consumed in the process.
ex:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) H = -890 kJ
2CH4(g) + 4O2(g)  2CO2(g) + 4H2O(l) H = -1780 kJ
S(s) + O2(g)  SO2(g) ΔHr = -296.9 kJ
SO2(g) + ½O2(g)  SO3(g) ΔHr = -98.3 kJ
SO3(g) + H2O(l)  H2SO4(l) ΔHr = -130.2 kJ
Net rxn : S(s) + 3/2O2(g) + H2O(l)  H2SO4(l)
ΔHr = (-296.9)+(-98.3)+(-130.2)
ΔHr = -525.4 kJ
Exercises:
1. Given the following thermochemical equations:
H2S(g) + 3/2O2  H2O(l) + SO2(g) Hr = -562.6 kJ
CS2(l) + 3O2(g)  CO2(g) + 2SO2(g) Hr = -1075.2 kJ
Calculate the value of Hr for the reaction:
CS2(l) + 2H2O(l)  CO2(g) + 2H2S(g)
2. Given the following thermochemical equations:
4NH3(g) + 3O2(g)  2N2(g) + 6H2O(l) ΔHr=-1531 kJ
N2O(g) + H2(g)  N2(g) + H2O(l) ΔHr=-367.4 kJ
H2(g) + ½O2(g)  H2O(l) ΔHr=-285.9 kJ
Calculate the value of ΔHΔHr for the reaction:
2NH3(g) + 3N2O(g)  4N2(g) + 3H2O(l)

2. The change in enthalpy of a reaction is equal in

magnitude but opposite in sign when the reaction is
reversed.
ex:
SO3(g) + H2O(l)  H2SO4(l) Hr = -130.2 kJ
H2SO4(l)  SO3(g) + H2O(l) Hr = 130.2 kJ

3. The enthalpy change for a reaction depends on the

state of the reactants & products.
ex:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) Hr = -890 kJ
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) Hr = -802 kJ

Measuring  H
 Direct Method
Hr = nHf(prod) -
-nHf(react)

Exercises:
1. Calculate Hr for the following:
a. C6H6(l) + 15/2O2(g)  6CO2(g) + 3H2O(l)
b. NH3(g) + HCl(g)  NH4Cl(s)
c. 2H2S(g) + 3O2(g)  2H2O(l) + 2SO2(g)

2. Calculate the heat of formation of OSCl 2(l) in the

following reaction:
OSCl2(l) + H2O(l)  SO2(g) + 2HCl(g) Hr = 10.3 kJ

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