Module No.

6 Energy Relationships in Chemical Reactions

The Nature of Energy and Types of Energy Energy is the capacity to do work or to transfer heats. Forms of Energy 1. Kinetic energy 2. Radiant energy 3. Thermal energy 4. Chemical energy . !otential energy Energy Changes in Chemical Reactions "eat # is the transfer of thermal energy $etween two $odies that are at different temperat%re. Thermochemistry is the st%dy of heat change in chemical reactions. Terms& 'ystem # part of the %ni(erse set aside for st%dy. '%rro%ndings # part of the %ni(erse o%tside the system Types of systems& 1. )pen system # can e*change mass and energy %s%ally in the form of heat with its s%rro%ndings. 2. Closed system # allows transfer of energy $%t not mass. 3. +solated system # does not allow the transfer of either mass or energy. Types of energy or heat transfer 1. E*othermic process # gi(es off heat to its s%rro%ndings E*ample& 2"2,g- . )2,g- / 2"2),l- . energy 2. Endothermic process # a$sor$s heat from its s%rro%ndings E*ample& Energy . 2"g),s- / 2"g,l- . )2,g000000000000000000000000000000000000000000000000000000000000000000000000000000000000 0 Practice Exercise 6.1 Tell whether the following is an open1 closed or isolated system. a. tree $. steel c. rice cooker d. coleman 2%g e. o(en f. electric fan g. a%tomo$ile h. hammer !ntroduction to Thermodynamics Thermodynamics

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" st%dy of the intercon(ersion of heat and other kinds of energy. Thermodynamic state of a system # defined $y a set of condition that completely specifies all the properties of the system1 s%ch as temperat%re1 press%re1 composition ,identity and amo%nt- and physical state ,gas1 li3%id1 solid-

State Function depends only on the state of the system and not on the way in which the came to be in that state ( !"! T# $ a chan%e in a state function describes a difference between two states& 't is independent of the process or pathway by which the chan%e occurs& () * )final $ )initial
The #irst $a% of Thermodynamics 'tatement& 1. Energy ca $e con(erted from one form to another1 $%t cannot $e created or destroyed. 2. The total energy of the isolated system is constant. 3. The s%m of all energy changes for all system participating in a process m%st $e 4ero. 5athematical 'tatement& Energy of the system . Energy of the s%rro%ndings 6 7 +nternal Energy ,E- # the total energy of the system d%e to potential and kinetic energies. 8E 6 Efinal 9 Einitial 8Eststem . 8s%rro%ndings 6 o 8Esystem 6 98Es%rro%ndings The change in internal energy1 E1 is determined $y the heat flow1 31 and the work1 w 8E 6 3 . w &ign Con'entions for (or) and *eat Process :ork done $y the system on the s%rro%ndings :ork done on the system $y the s%rro%ndings "eat a$sor$ed $y the system from the s%rro%ndings "eat a$sor$ed $y the s%rro%ndings from the system

&ign ; . . ;

0000000000000000000000000000000000000000000000000000000000000000000000000000000000 Practice Exercise 6.+ The work done when a gas is compressed in a cylinder is 4<2=. >%ring the process1 there is a heat transfer of 12?= from the gas to the s%rro%ndings. Calc%late the energy change for this process.

(or) +n most chemical and physical changes1 the only kind of work is press%re9(ol%me work. For gas e*pansion against a constant e*ternal press%re

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! ! 8@

gas

: 6 9 !8@ 000000000000000000000000000000000000000000000000000000000000000000000000000000000000 0 Practice Exercise 6.+ A sample of gas e*pands $y 22.4B against an a(erage press%re of 2. atm. "ow m%ch work ,k=- is done in the processC +s the work done $y the system or $y the s%rro%ndingC

&pecial Cases of Processes 1. Constant @ol%me !rocess D@ 6 7E !D@ 6 7 Therefore& DE 6 3(

2. Constant !ress%re !rocess DE 6 3 . w 6 3p 9 !D@ 3p 6 DE . !D@ Enthalphy, * # the s%m of internal energy and work. " 6 E . !@ D" 6 DE . D,!@At constant press%re Enthalphy of Reactions D" 6 DE . !D@

For any reaction of the type Reactants / !rod%cts 8" 6 " ,prod%cts- # " ,reactants-

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Thermochemical E-uations A thermochemical e3%ation e*presses the following& 1. :eight relationships 2. !hysical states of reactant and prod%cts 3. Temperat%re 4. !ress%re . "eat e(ol(ed or a$sor$ed in the reaction Characteristics of 8"r*n .& For any reaction1 8"r*n 6 F" ,prod%cts- # F" ,reactants2. +t depends on the state of the s%$stance "2,g- . G )2,g- / "2) ,l8" 6 92? .? k= "2,g- . G )2,g- / "2) ,g8" 6 9241.? k= 3. +t is proportional to the amo%nt of reactants and prod%cts "2,g- . G )2,g- / "2) ,l8" 6 92? .? k= 2"2,g- . )2,g- / 2 "2) ,l8" 6 9 H1.< k= 4. +t changes sign when a process is re(erse "2) ,l- / "2,g- . G )2,g8" 6 .2? .? k= ......................................................................... Practice Exercise 6./ Calc%late the heat in(ol(ed when H4.<g of ') 2 ,molar mass 6 <4.7HgImol- is con(erted to ')3. Thermochemical reaction& ')2,g- . G)2,g- ')3,gD" 6 9JJ.1k=Imol

Comparison of 0* and 0E DE 6 D" 9 !D@ For the process in(ol(ing gases1 from the ideal gas law e3%ation& !@ 6 nRT !D@ 6 8nRT DE 6 D" 9 DnRT Dn 6 no. of moles of gases in the prod%cts # no. of moles of gases in the reactants Practice Exercise 6.1 Calc%late the change in internal energy when 2 moles of C) are con(erted to 2 moles of C)2 at 1 atm and 2 oC. 2C),g- . )2,g- 2C)2,gD" 6 9 <<.7k=Imol

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Practice Exercise 6.2 For which of the following reactions is D" a$o%t the same as DE& a- 2C%,s- . ',s- C%2',s$- K,3- . )2,s- 2K),3c- 'i)2,s- . ',s- 3C,s- . 2C),3d- C"3)",s- . ',s- C),3Calorimetry 9 e*perimental techni3%es of determining the amo%nt of energy ,heat- associated with any chemical or physical processes. 9 $ased on o$ser(ing the temperat%re change when a system a$sor$s or releases energy in the form of heat. 'pecific heat of a s%$stance1 s # amo%nt of heat re3%ired to raise the temperat%re of one gram of the s%$stance one degree Celsi%s ,or one Kel(in- with no change in phase. +t has a %nits =Ig. oC "eat capacity of a $ody1 C # the amo%nt of heat re3%ired to raise its temperat%re 1 oC. +ts %nits are =IoC. :here m 6 mass of s%$stance in grams.

0 * ms

Calc%lating heat change

1 * ms(t 1 * 0(t

:here 8t 6 tfinal 9 tinitial

000000000000000000000000000000000000000000000000000000000000000000000000000000000000 0 Practice Exercise 6.6 A 4<<g sample of water is heated from ?. 7 oC to H4.<7oC. Calc%late the amo%nt of heat a$sor$ed ,in kilo2o%les- $y the water.

Calorimeter 9

apparat%s %sed to determine the heat of reaction

T3PE& 4# C5$4R!METER Constant"6olume Calorimetry # %sed to determine the heat of com$%stion.

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3cal . 3r*n 6 7 3r*n 6 9 3cal 3cal 6 Ccal8t where& Ccal 6 heat capacity of calorimeter 8t 6 change in temperat%re 0000000000000000000000000000000000000000000000000000000000000000000000000000000000000 0 Practice Exercise 6.7 A 3%antity of 1.43 g of naphthalene C 17"?1 a p%ngent9smelling %sed in moth repellants1 was $%rned in a constant9(ol%me $om$ calorimeter. Conse3%ently1 the temperat%re of the water rose from 27.2?oC to 2 .J oC. +f the heat capacity of the $om$ pl%s water was 17.1Hk=I oC1 calc%late the heat com$%stion of naphthalene on a molar $asisE that is1 find the molar heat of com$%stion. ,molar mass of C17"? 6 12?.2g-

Constant"Pressure Calorimetry # %sed to meas%re 3! for reactions in sol%tion at constant press%re

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Practice Exercise 6.8 A 3%antity of 1.77 * 172 mB of 7. 5 "Cl was mi*ed with 1.77 * 17 2 mB of 7. 5 Ka)" in a constant9press%re calorimeter of negligi$le heat capacity. The initial temperat%re of the "Cl and Ka)" sol%tions was the same1 22. oC1 and the final temperat%re of the mi*ed sol%tion was 2 .?< oC. Calc%late the heat change for the ne%trali4ation reaction on a molar $asis. Ka)",a3- . "Cl,a3- KaCl,a3- . "2),lAss%me that the densities and specific heats of the sol%tions are the same as for water ,1.77gImB and 4.1?4=Ig L oC1 respecti(ely-

&tandard Enthalpy of #ormation and Reaction The thermodynamic standard state of a s%$stance is its most sta$le p%re form %nder standard press%re ,1 atm- and some specific temperat%re ,2 oC or 2J? K %nless specified'tandard molar enthalphies of formation1 0*fo 9 energy released or a$sor$ed when one mole of a compo%nd is formed from its elements For element and diatomic elements s%ch as "21 K21 )21 Cl21 F21 Mr2 0*fo 9 : 'tandard enthalpy of reaction1 0*rxno " energy released or a$sor$ed as a res%lt of the complete chemical reaction of the reactants D"ro 6 ND"fo ,prod%cts- 9 ND"fo ,reactantsThe ;irect Method

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Ose of ta$le of 'tandard Enthalphies of Formation to calc%late enthalphies of reactions D"ro 6 ND"fo ,prod%cts- 9 ND"fo ,reactants0000000000000000000000000000000000000000000000000000000000000000000000000000000000000 0 Practice Exercise 6.< Calc%late the standard heat of reactions1 8"o1 for the following %sing standard heat of formation data 8"or. a. CaC)3,s- Ca),s- . C)2,g-

$. 2K),g- . )3,g- K)2,g- . )2,g-

The !ndirect Method Mased on "essPs Baw of heat s%mmation which states thatE :hen a reactants are con(erted to prod%cts1 the change in enthalpy is the same whether the reaction takes place in one step or in a series of steps. 000000000000000000000000000000000000000000000000000000000000000000000000000000000000 0 Practice Exercise 6.1: Qi(en the following thermochemical e3%ations& 4K"3,g- . 3)2,g- 2K2,g- . <"2),lD"o 6 91 31k= K2),g- . "2,g- K2,g- . "2) ,lD"o 6 93<H.4k= "2,g- . G)2,g- "2),lD"o 6 92? .Jk= Calc%late the (al%e of D"o fro the reaction 2K"3,g- . 3K2),g- 4K2,g- . 3"2),l-

&ol'e Pro=lems <.1 1 <.1H1 <.2 1 <.2H1 <.331 <.3H1 <. 11 <.<11 <.<3 E pages 1J? # 271 Qeneral Chemistry& The Essential Concepts1 th edition $y Raymond Chang References Qeneral Chemistry& The Essential Concepts1 th edition $y Raymond Chang Chemistry & ?th edition $y :hitten1 >a(is1 !eck and 'tanley CHEMISTRY: The Molecular Nature of Matter and Change 1 4th ed. $y 5artin 'il$er$erg

Chemistry: The General Science, 10th ed, by Brown, Le May and Bursten

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