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Thermochemistry

Energy is the capacity to do work Radiant energy comes from the sun and is earths primary energy source

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 Potential energy is the energy available by virtue of an objects position

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6.1

Energy hanges in

hemical !eactions

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

"##

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$## greater thermal energy

6.%

Thermochemistry is the study of heat change in chemical reactions.

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open closed energy

The system is the specific part of the universe that is of interest in the study.

isolated nothing
6.%

Exchange: mass ' energy

Exothermic process is any process that gives off heat ( transfers thermal energy from the system to the surroundings. %)% *g+ , -% *g+ )%- *g+

Endothermic process is any process in which heat has to be supplied to the system from the surroundings. energy , %)g- *s+ %)g *l+ , -% *g+ )%- *l+
6.%

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energy , )%- *s+

%)%- *l+ , energy

)%- *l+ , energy

E.othermic

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Endothermic

6.%

Thermodynamics is the scientific study of the interconversion of heat and other kinds of energy.

energy/ pressure/ volume/ temperature

0otential energy of hiker 1 and hiker % is the same even though they took different paths.

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State functions are properties that are determined by the state of the system/ regardless of how that condition was achieved.

E & Efinal 2 Einitial

P & Pfinal 2 Pinitial V & Vfinal 2 Vinitial

T & Tfinal 2 Tinitial

6.1

hemical energy lost by combustion & Energy gained by the surroundings system surroundings 6.1

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Esystem , Esurroundings & #
or

First law of thermodynamics ( energy can be converted from one form to another/ but cannot be created or destroyed.

Esystem & -Esurroundings

)3 , 4-%

1 -% , $)%-

E.othermic chemical reaction5

6nother form of the first law for Esystem

E & q , w q is the heat e.change between the system and the surroundings w is the work done on *or by+ the system w & 2PV when a gas e.pands against a constant e.ternal pressure E is the change in internal energy of a system

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6.1

7ork 8one -n the 9ystem

w&Fxd w & 2P V PxV=

F 3 x d =Fxd=w 2 d

7ork is not a state function5

w & wfinal 2 winitial

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initial final

: ; #

-PV < 0 wsys < #

6.1

*a+

V & 4.$ = ( 1.6 = & 1.3 =

W & 2# atm . 1.3 = & # =atm & # joules *b+

V & 4.$ = ( 1.6 = & 1.3 =

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w & 2P V P & # atm w & 21$.1 =atm .

6 sample of nitrogen gas e.pands in volume from 1.6 = to 4.$ = at constant temperature. 7hat is the work done in joules if the gas e.pands *a+ against a vacuum and *b+ against a constant pressure of 1.> atm?

P & 1.> atm

w & 21.> atm . 1.3 = & 21$.1 =atm 1#1.1 @ & 21$1# @ 1=atm
6.1

Chemistry in Action: Making Snow

E & q , w
q&#

w < #/ E < #

E & T

T < #/ 9A-75

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Enthalpy and the Birst =aw of Thermodynamics

E & q , w

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q & ! and w & 2PV E & ! 2 PV ! & E , PV

6t constant pressureC

6.$

Enthalpy (H is used to Duantify the heat flow into or out of a system in a process that occurs at constant pressure.

! & ! *products+ ( ! *reactants+

! & heat given off or absorbed during a reaction at constant pressure

!products < !reactants ! < #

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!products ; !reactants ! ; #

6.$

Thermochemical EDuations
Es ! negative or positive?

6.#1 k@ are absorbed for every 1 mole of ice that melts at ## and 1 atm. )%- *s+ ) % - *l + ! & 6.#1 k@
6.$

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! ; #

9ystem absorbs heat Endothermic

Thermochemical EDuations
Es ! negative or positive?

3"#.$ k@ are released for every 1 mole of methane that is combusted at %4# and 1 atm. )$ *g+ , %-% *g" -% *g" # %)%- *l+ ! & 23"#.$ k@
6.$

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! < #

9ystem gives off heat E.othermic

Thermochemical EDuations
The stoichiometric coefficients always refer to the number of moles of a substance

Ef you reverse a reaction/ the sign of ! changes )%- *l+ ) % - *s + ! & 26.#1 k@

Ef you multiply both sides of the eDuation by a factor n/ then ! must change by the same factor n. %)%- *s+ %)%- *l+ ! & % . 6.#1 & 1%.# k@

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)%- *s+ ) % - *l +

! & 6.#1 k@

6.$

Thermochemical EDuations
The physical states of all reactants and products must be specified in thermochemical eDuations.

)%- *l+

)ow much heat is evolved when %66 g of white phosphorus *0$+ burn in air? 0$ *s+ , 4-% *g+
%66 g 0$

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)%- *s+ ) % - *l + )%- *g+ 0$-1# *s+ . .
1 mol 0$ 1%1." g 0$

! & 6.#1 k@

! & $$.# k@

! & 21#11 k@

1#11 k@ & 6$># k@ 1 mol 0$ 6.$

6 omparison of ! and E
%Aa *s+ , %)%- *l+ E & ! 2 PV %Aa-) *aq+ , )% *g+ ) & 216>.4 k@Fmol 6t %4 # / 1 mole )% & %$.4 = at 1 atm

PV & 1 atm . %$.4 = & %.4 k@

E & 216>.4 k@Fmol ( %.4 k@Fmol & 21>#.# k@Fmol

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6.$

The specific heat *s+ of a substance is the amount of heat * q+ reDuired to raise the temperature of one gram of the substance by one degree elsius. The heat capacity *C+ of a substance is the amount of heat *q+ reDuired to raise the temperature of a given quantity *m+ of the substance by one degree elsius. &mxs

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)eat *q+ absorbed or releasedC q & m x s x t q& x t t & tfinal 2 tinitial

6.4

)ow much heat is given off when an 36" g iron bar cools from "$# to 4# ? s of Be & #.$$$ @Fg # t & tfinal ( tinitial & 4#

q & mst & 36" g . #.$$$ @Fg #

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( "$# & 23"# . (3"#

& 21$/### @

6.4

onstant2:olume alorimetry

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Ao heat enters or leaves5

qsys & qwater , qbomb , qr.n

qsys & # qr.n & 2 *qwater , qbomb+

$om$

qwater & m x s . t qbomb & x t

!eaction at onstant V ! & qr.n ! G qr.n

6.4

onstant20ressure

alorimetry

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qcal & Ao heat enters or leaves5

qsys & qwater , qcal , qr.n

qsys & # qr.n & 2 *qwater , qcal+

%al

qwater & m x s . t x t

!eaction at onstant P ! & qr.n

6.4

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6.4

Chemistry in Action:
Buel :alues of Boods and -ther 9ubstances
)1%-6 *s+ , 6-% *g+ 6 -% *g+ , 6)%- *l+ ) & 2%3#1 k@Fmol

1 cal & $.13$ @ 1 al & 1### cal & $13$ @ 9ubstance 6pple Heef Heer Iasoline

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!%om$ustion *k@Fg+
2% 23 21.4 21$

Hecause there is no way to measure the absolute value of the enthalpy of a substance/ must E measure the enthalpy change for every reaction of interest? Establish an arbitrary scale with the standard enthalpy of formation *)# f + as a reference point for all enthalpy e.pressions. Standard enthalpy of formation *)#f+ is the heat change that results when one mole of a compound is formed from its elements at a pressure of 1 atm. The standard enthalpy of formation of any element in its most stable form is Jero. )#f *-%+ & # )#f *-1+ & 1$% k@Fmol )#f * / graphite+ & # )#f * / diamond+ & 1."# k@Fmol
6.6

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Pe U rso se n a W lu IS se EL o Y nly !!! .

6.6

# The standard enthalpy of reaction *)r.n + is the enthalpy of a reaction carried out at 1 atm.

# # *6+ $ ) )r.n , & K %)#f * + , d)#f *8+ L 2 K a)# f f *H+ L # )r.n & n)#f *products+ 2 m)f# *reactants+

Hess!s "aw# 7hen 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. Et doesnt matter how you get there/ only where you start and end.+
6.6

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a6 , $H

% , d8

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*graphite+ , 1F%-% *g+

- *g+ -% *g+ -% *g+

- *g+ , 1F%-% *g+

*graphite+ , -% *g+

6.6

alculate the standard enthalpy of formation of 9% *l+ given thatC # *graphite+ , -% *g+ -% *g+ )r.n & 21"1.4 k@

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-% *g+ , %9-% *g+
*graphite+

9*rhombic+ , -% *g+ 9%*l+ , 1-% *g+

9-% *g+

# )r.n & 2%"6.1 k@

)# r.n & 21#>% k@ 9%

1. 7rite the enthalpy of formation reaction for , %9*rhombic+

9 % *l +

%. 6dd the given r.ns so that the result is the desired r.n. , -% *g+ %9*rhombic+ , %-% *g+
*graphite+
# -% *g+ )r.n & 21"1.4 k@ # %9-% *g+ )r.n & 2%"6.1.% k@

-%*g+ , %9-% *g+

*graphite+

9% *l+ , 1-% *g+

)# r.n & ,1#>% k@

6.6

, %9*rhombic+ 9 % *l + )# & 21"1.4 , *%.2%"6.1+ , 1#>% & 36.1 k@ r.n

)6 *l+ , 14-% *g+

# )r.n & n)#f *products+ 2 m)f# *reactants+ # # # )r.n & K 1%)# f * -%+ , 6)f *)%-+L 2 K %)f *

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24"$6 k@ & 2 %">1 k@Fmol % mol
6

HenJene * 6)6+ burns in air to produce carbon dio.ide and liDuid water. )ow much heat is released per mole of benJene combusted? The standard enthalpy of formation of benJene is $".#$ k@Fmol. 1% -% *g+ , 6)%- *l+

)6+ L

# )r.n & K 1%.(1"1.4 , 6.(13>.6 L ( K %.$".#$ L & 24"$6 k@

)6

6.6

Chemistry in Action: Bom ardier Beetle !efense

6

)$*-)+% *aq+ , )%-% *aq+

6

)$-% *aq+ , %)%- *l+ !0 & ?

)$*-)+% *aq+

)%-% *aq+

)% *g+ , M -% *g+

!0 & 1>> 2 "$.6 ( %36 & 2%#$ k@Fmol

E.othermic5

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)$-% *aq+ , )% *g+ !0 & 1>> k@Fmol

)%- *l+ , M-% *g+ !0 & 2"$.6 k@Fmol )%- *l+ !0 & 2%36 k@Fmol

The enthalpy of solution *Hsoln+ is the heat generated or absorbed when a certain amount of solute dissolves in a certain amount of solvent.

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!soln & !soln 2 !components

7hich substance*s+ could be used for melting ice?

7hich substance*s+ could be used for a cold pack?

6.>

The 9olution 0rocess for Aa l

!soln & 9tep 1 , 9tep % & >33 ( >3$ & $ k@Fmol

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6.>