An Introduction to Thermochemistry

The Laws of Conservation of Energy states that: the total energy of the universe is a
constant; energy cannot be created or destroyed.
First Law of Thermodynamics:
Universe = System + Surroundings
Euniverse = Esystem + Esurroundings = 0
Open system open to the surroundings.
Closed system closed to the surroundings.
Types of Energy:
1. Kinetic Energy: the energy o motion.
. !otentia" energy: stored energy.
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E 1 O ) 1 #
Ca"cu"ating $eat Transfer
The ormula or calculating heat transer is as ollo*s: % & m ' c ' (T
+here , is the amount o heat in - ./oules01 m is the mass in g .grams01 c is the speciic heat
capacity in -2g3C .the values or this varia4le are usually ound in a ta4le01 and T is the change
in temperature in 3C .degrees Celsius0. #oreover1 1 *hich is called 5elta1 means 6change in17
and in this case: 6change in7 temperature.
Things to )emem*er:
Energy and heat are the same.
$ mass dou4les1 so does heat8
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E O ) 1 #
+uestions for Ca"cu"ating $eat Transfer
9. 900 g o Ethanol at :;3C is heated until it reaches ;03C. !o* much heat does the ethanol
gain<
, = m = c = T m = 900 g
, = .900 g0.:.>? -2 g3C0.:;3C0 (T = :;3C
, = ?9;0 - c = :.>? -2 g3C
% = < ?9;0 -
:. @eaAer ' contains ;0 g o li,uid at room temperature. The 4eaAer is heated until the li,uid
gains 903C. @eaAer @ contains 900 g o the same li,uid at room temperature. This 4eaAer is
also heated until the li,uid gains 903C. $n *hich 4eaAer does the li,uid a4sor4 the most heat<
,ea-er A
, = m = c = T m = ;0 g
, = .;0 g0.>.9B> -2 g3C0.903C0 (T = 903C
, = :0C: - c = >.9B> -2 g3C
% = < :0C: -
,ea-er ,
, = m = c = T m = 900 g
, = .900 g0.>.9B> -2 g3C0.903C0 (T = 903C
, = >9B> - c = >.9B> -2 g3C
% = < >9B> -
. +hen your mass .g0 dou4les1 then so does your heat8
D. !o* much heat is re,uired to raise the temperature o EBC g o li,uid ammonia rom :;.03C
to B:.E3C< "emem4er to su4tract B:.E3C rom :;.03C to determine T1 as *e usually do not use
negative temperatures1 yet.
, = m = c = T m = EBC g
, = .EBC g0.>.E0 -2 g3C0.;E.E3C0 (T = ;E.E3C
, = :9DC?B.C9 - c = >.9B> -2 g3C
, = :9> F/ % = < :9> F/
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E / O ) 1 #
. "emem4er i the inal num4er or 6,7 is large1 you can convert it to F/ .Ailo/oules0 4y using the
very elementary 6F!5GHdcm7. $ you are going let1 then divide 4y 90001 i you are going right1
then multiply 4y 9000.
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E 0 O ) 1 #
Entha"py
The change in heat1 speciic to phase change I changing state rom solid to li,uid1 etc. I that
does not involve temperature change.
1111111111 23,LI4I5ATI65 1111111111
melting 4oiling2vaporiJing
2o"id 111117 Li%uid 111117 8as
911111 911111
solidiying2reeJing condensing
1111111111 23,LI4I5ATI65 1111111111
The ormula or calculating enthalpy is as ollo*s: $ & n ' ($
+here ! is the enthalpy change in F/ .Ailo/oules01 n is the num4er o moles in mols1 and !
.vaporiJation1 condensation1 melting1 reeJing1 etc.0 is the molar enthalpy in F/2mol. #oreover1
the value or ! is usually ound in a ta4le that is already provided1 or easily ound.
4o"ar Entha"py of :apori;ation<,oi"ing= ($vap:
The enthalpy change or the state change o one mole rom li,uid to gas.
4o"ar Entha"py of Condensation= ($cond:
The enthalpy change or the state change o one mole o a su4stance rom gas to a li,uid.
4o"ar Entha"py of 4e"ting= ($me"t:
The enthalpy change or the state change o one mole o a su4stance rom solid to li,uid.
4o"ar Entha"py of Free;ing= ($fre:
The enthalpy change or the state change o one mole o a su4stance rom li,uid to solid.
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E > O ) 1 #
+uestions for Entha"py Change
9. 'n ice cu4e *ith a mass o B.: g is placed in some lemonade. The ice cu4e melts. !o* much
heat does the ice cu4e a4sor4 rom the lemonade as it melts<
B.: g o !:0 =
9 mol
9B.0: g
= 0.>? mols o !:0
! = n = ! $ = < :.EE F/
! = .0.>? mols0.?.0: F/2mol0 n = 0.>? mols
! = :.EE F/ ($ = ?.0: F/2mol
:. +hat mass o 5iethly Ether1 C>!90O1 can 4e vaporiJed 4y adding B0.E F/ o heat<
! = n = ! $ = B0.E F/
B0.E F/ = n .:C F/2mol0 n = < :.EB mols
B0.E F/ K :C F/2mol = n ($ = :C F/2mol
:.EB mols = n
:.EB mols o C>!90O =
E>.9 g
9 mol
= :0;.CCB g o C>!90O
= :0? g o C>!90O
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E ? O ) 1 #
Tota" Energy Changes
Things to )emem*er:

The values o 6c7 changes 4ased on its physical state .6,70 on the curve.

"emem4er that1 *hen you are dra*ing2determining Total Energy Changes .Curves01 use
the ollo*ing ormulas: , = m = c = T @ ! = n = !.
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E # O ) 1 #
+uestions for Tota" Energy Changes
9. ' metal 4ucAet containing ;D:.9 g o ice at 03C is placed on a *oodL4urning stove. The ice is
melted and then heated to >;.:93C.
AaB 5ra* a heating curve.
A*B !o* much heat is re,uired to melt the ice and *arm the *ater to >;.:93C<
AaB
, = m = c = T m = ;D:.9 g
, = .;D:.9 g0.>.9B> -2g3C0.>;.:9 3C0 (T = >;.:93C
, = 900?;9.D9: - c = >.9B> -2g3C
, = 900.E F/ % = < 900.E F/
! = n = ! $ = < 9EE.E F/
! = .:C.;: mol0.?.0: F/2mol0 n = :C.;: mol
! = 9EE.E F/ ($ = ?.0: F/2mol
;D:.9 g o !:O =
9 mol
9B.0: g
= :C.;: mols o !:O
A*B
Etotal = , + !
Etotal = 900.E F/ + 9EE.E F/
Etotal = :EB.> F/
:. Calculate the total heat released *hen :00 g o *ater vapor at D00.03C is cooled until it
reaches L:0.03C. The speciic heat capacity o ice is :.09 -2g3C. The speciic heat capacity o
*ater vapor is :.09 -2g3C.
AaB 5ra* a heating curve.
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E C O ) 1 #
+uestions for Tota" Energy Changes ContinuedD
AaB
,9 = m = c = T m = :00 g
,9 = .:00g0.:.09 -2g3C0.:003C0 (T = :003C
,9 = B0>00 - c = :.09 -2g3C
,9 = B0.> F/ %1 = < B0.> F/
!9 = n = ! $1 = < >;9.EE F/
!9 = .99.9 mols0.>0.E F/2mol0 n = 99.9 mols
!9 = >;9.EE F/ ($ = >0.E F/2mol
,: = m = c = T m = :00 g
,: = .:00g0.:.09 -2g3C0.:00 (T = 9003C
,: = >0:00 - c = :.09 -2g3C
,: = >0.: F/ %1 = < >0.: F/
!: = n = ! $ = < ??.B: F/
!: = .99.9 mols0.?.0: F/2mol0 n = 99.9 mols
!: = ??.B: F/ ($ = ?.0: F/2mol
,D = m = c = T m = :00 g
,D = .:00g0.:.09 -2g3C0.L:0.03C0 (T = >;.:93C
,D = LB0>0 - c = >.9B> -2g3C
,D = LB.0> F/ %/ = < LB.0> F/
,D = + B.0> .*e are only using + right no*0
:00 g o !:O =
9 mol
9B.0: g
= 99.9 mols o !:O
Etotal = ,9 + h9 + ,: + h: + ,D
Etotal = B0.> F/ + >;9.EE F/ + >0.: F/ + ??.B: F/ + B.0> F/
Etotal = ?>E.:D F/
Things to )emem*er:

)or ,uestions such as the one eatured a4ove1 repeat 6, = m = c = T @ ! = n = !7 until

there are no more 6,M7 or 6!M7 to solve or. #oreover1 remem4er that the values o 6c7
changes 4ased on its physical state .6,70 on the curve.
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E E O ) 1 #
Ca"orimetry
Calorimetry is a *ay o measuring changes in Ainetic energy using an iso"ated system.
2imp"e Ca"orimeter ACoffee1CupB:
!system = ,*ater
n = ! = m = c = T
+here n is the num4er o moles in mols1 and ! .vaporiJation1 condensation1 melting1 reeJing1
etc.0 is the molar enthalpy in F/2mol1 m is the mass in g .grams01 c is >.9B> -2g3C1 and T is the
change in temperature in 3C .degrees Celsius0.
Things to )emem*er:
Simple Calorimeters al*ays involves *ater. 'ny talA o *ater .*arming or cooling0 in your
,uestion means you are using a Simple Calorimeter.

%ou are usually always solving or 6n7 or 6!7.

The value o 6c7 *ill always 4e >.9B> -2g3C in a Simple Calorimeter.

$solated2dissolving = *arming *ater.
'l*ays include !system = ,*ater a4ove your ormula.
,om* Ca"orimeter:
!system = ,cal
n = ! = C = T
+here n is the num4er o moles in mols1 and ! .vaporiJation1 condensation1 melting1 reeJing1
etc.0 is the molar enthalpy in F/2mol1 C is the speciic heat capacity o the calorimeter in F/23C1
and T is the change in temperature in 3C .degrees Celsius0.
Things to )emem*er:
@om4 Calorimeters never involve *ater.

%ou are usually always solving or 6n7 or 6!7.

'l*ays include !system = ,cal a4ove your ormula.
Com4ustion is usually involved *ith @om4 Calorimeters.
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E 1 F O ) 1 #
+uestions for Ca"orimetry
9. Suppose >.? o NiCl is dissolved in D: ml o *ater. The *ater had an initial temperature o
::3C1 *hich increased to BE.:3C *hen the reaction completed. Calculate the molar enthalpy o
the NiCl.
!system = ,*ater n = 0.99 mols
n = ! = m = c = T ($ = <
.0.99 mols0 ! = .D: g0. >.9B> -2g3C0. ?;.:3C0 m = D: ml .D: g0
! = BE:C.;0 - K 0.99 mols c = >.9B> -2g3C
! = ECD;C.0E -2mol (T = ?;.:3C
! = LEC.D? F/2mol
>.? g o NiCl =
9 mol
>:.> g
= 0.99 mols o NiCl
:. The molar enthalpy o com4ustion or a gasoline assumed to 4e octane .CB!9B0 is L9.D
#/2mol. ' particular engine has a heat capacity o 90; F/23C. +hat is the minimum mass o
octane that must 4e 4urned to change the temperature o an engine rom 9B3C to 9:03C<
!system = ,cal n = <
n = ! = C = T ($ = L9.D #/2mol .L9D00 F/2mol0
n .L9D00 F/2mol0 = .90; F/23C0. 90:3C0 C = 90; F/23C
n = 90E90 F/ K L9D00 F/2mol (T = 90:3C
n = LB.:> mols
n = B.:> mols
B.:> mols o CB!9B =
99>.:? g
9 mol
= C>9.;0 g o CB!9B
Things to )emem*er:

EOothermic (ives o heat .$ncrease Temp0.$ncrease T0 I ! is negative

Endothermic TaAes in heat .5ecrease Temp0.5ecrease T0 I ! is positive

U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E 1 1 O ) 1 #
$essGs Law of $eat 2ummation
Chemists can determine the enthalpy change o any reaction using an important la*1 Ano*n as
$essGs "aw of heat summation1 *hich states: the enthalpy change o a physical or chemical
process depends only on the 4eginning conditions .reactants0 and the end conditions
.products0. The enthalpy change is independent o the path*ay o the process and the num4er
o intermediate steps in the process. $t is the sum o the enthalpy changes o all the individual
steps that maAe up the process.
Things to )emem*er:
%ou are trying to o4tain an overall ormula that is the same as your 6Target7.

%ou may need to multiply or divide one o your 6(ivens7.

%ou may need to reverse one o your 6(ivens17 4ut i you do1 4e sure to change the sign o
the 6($Hr7. )or eOample: i it is +;0 F/1 you must change it to L;0 F/1 and viceLversa.
@e sure to *atch *hat state each compound is in ..g01 .l01 .s00. The ,uestion you are 4eing
asAed may try to tricA you8
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E 1 O ) 1 #
+uestions for $essGs Law of $eat 2ummation
9. Target: :PO .g0 + O: .g0 P:O> .g0 ($Hr = <
8iven: .90 P:O> .g0 :PO: .g0 ($Hr = +;B F/
.:0 PO .g0 + Q O: .g0 PO: .g0 ($Hr = L ;? F/
.:0 :.PO .g0 + Q O: .g0 PO: .g0 ($Hr = L ;? F/0
.:0 :PO .g0 + O: .g0 :PO: .g0 ($Hr = L 99: F/
rev .90 :PO: .g0 P:O> .g0 ($Hr = L ;B F/
:PO .g0 + O: .g0 :PO: .g0 ($Hr = L 99: F/
:PO: .g0 P:O> .g0 ($Hr = L ;B F/
LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL
:PO .g0 + O: .g0 P:O> .g0 ($Hr = L 9E0 F/
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E 1 / O ) 1 #
$essGs Law of $eat 2ummation AFormationsB
!essRs Na* o !eat Summation .)ormations0 is used to calculate ! or a balanced chemical
e,uation.
!3rOn = S.n = !3

products0 L S.n = !3

reactants0
+here !3rOn is the reaction and is in F/1 S simply means the 6Sum o71 n is the num4er o mols
rom the 4alanced chemical e,uation1 !3

products is the standard heat o ormation or each o
the products listed in F/2mol1 and !3

reactants is the standard heat o ormation or each o the
reactants listed in F/2mol.
Things to )emem*er:

The values o 4oth 6!3 products7 and 6!3 reactants7 are ound in ta4les. $ 6!3

products7 or 6!3

reactants7 are listed in the &eriodic Ta4le1 then the value is automatically
Jero8
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E 1 0 O ) 1 #
+uestions for $essGs Law of $eat 2ummation AFormationsB
9. C:!> .g0 + !:.g0 C:!?.g0 ($ = <
!3rOn = S.n = !3

products0 L S.n = !3

reactants0
!3rOn = G 9.LB>.E F/2mol0 H I G 9.;:.D F/2mol0 + 9.0 F/2mol0 H
!3rOn = G LB>.E F/2mol H I G ;:.D F/2mol H
!3rOn = L B>.E F/2mol L +;:.D F/2mol
!3rOn = L9DE F/
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E 1 > O ) 1 #
$essGs Law of $eat 2ummation A!otentia" Energy IiagramsB
EJothermic )eaction
&roducts must have a lo*er energy .F/0 than
reactants .high0.
Endothermic )eaction
&roducts must have a higher energy .F/0
than reactants .lo*0.
Things to )emem*er:
$ the products are 4elo* the reactants1 then your value o !3rOn *ill 4e negative. $ the
products are a4ove the reactants1 then your value o !3rOn *ill 4e positive.
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E 1 ? O ) 1 #
+uestions for $essGs Law of $eat 2ummation A!otentia" Energy
IiagramsB
9. C:!> .g0 + !:.g0 C:!?.g0 ($ = <
!3rOn = S.n = !3

products0 L S.n = !3

reactants0
!3rOn = G9.LB>.E F/2mol0H I G9.;:.D F/2mol0 + 9.0 F/2mol0H
!3rOn = GLB>.E F/2molH I G;:.D F/2molH
!3rOn = L B>.E F/2mol L +;:.D F/2mol
!3rOn = L9DE F/
U N I T 7 : T ! E " # O C ! E # $ S T " % & ' ( E 1 # O ) 1 #