Chemistry 3 First Quarter

CHEMICAL KINETICS Kinetics deals with rates and the stepwise molecular events by which a reaction occurs Ways of Expressing Reaction Rates: 1. Appearance of roduct A!

+omponents 1. +onstant ". 1rder 2. +oncentration

3actors Affecting the Rate of Reaction: 1. hysical 4tate ". +oncentration of Reactants 2. 5emperature 6. resence of +atalyst 5heoretical 7odels of Kinetics 1. +ollision 5heory particles must collide in order to react collision fre)uency & reaction rate $neffective +ollision: collisions that do not create reactions explains the effect of temperature and concentration on the rate of reaction 8activation energy and order ". 5ransition 4tate 5heory hypothetical species believed to exist in an intermediate state that lies between the reactants and products 9transition state or activated complex:

". #isappearance of Reactant A! Rates 1. $nstantaneous Rate % rate in a particular moment int the reaction. % tangent line ". $nitial Rate % rate at t & '. (eneral E)uation: aA * b! * c+ * d# rate:

RATE LAW AND ITS COMPONENTS Rate ,aw % expresses rate as a function of reactant and product concentration- and temperature % rate & ./A0m/!0n- where m and n are the orders- determined experimentally 1rder of Reaction % determined by: 1. method of initial rates ". linear regression 2. substituting values into integrated e)uations to find the e)uation that gives a constant value ..

REACTION MECHANISMS % steps in an overall reaction % (iven overall reaction: "A * ! E * 3: 91: A * ! + 9": + * A # 92: #E*3 %%%%%%%%%%%%%%%%%%%%%%%%% "A * ! E * 3

//alyssaboller

Chemistry 3 First Quarter

% Elementary 4teps simplest steps in reaction mechanism cannot be bro.en down to simpler steps described by molecularity 9number of particles:
Elementary 4tep

rate1 & .1/<1"0/3"0 rate" & ."/<1"0/30 7echanism with 3ast $nitial 4tep 91: <19g: * 12(g) <129g: 9fast: 9": <129g: * <19g: "<1" 9slow: experimentally determined rate: rate & ./<10"/12] a: 1verall Reaction: "<19g: * 1" "<1"9g: b: 7olecularity of each step: 91: !imolecular 9": !imolecular c: Rate law for each step rate1 & .1/<10/1"0 rate" & .%1/<120 rate2 & .2/<120/<10 d: 1verall Rate ,aw of Reaction 4olution: .1/<10/1"0 & .%1/<120 /<120 & /<10/1"0

7olecularity ;nimolecular !imolecular !imolecular 5ermolecular

Rate ,aw Rate & ./A0 Rate & ./A0" Rate & ./A0/!0 Rate & ./A0"/!0

A product "A product

A * ! product
"A * ! product

Rate%determining 4tep of a Reaction 7echanism slowest step represents the rate law of the overall reaction Example: <1"9g: * +19g: <19g: * +1"9g: rate by elementary step: rate & ./<1"0/+10 experimentally determined rate: rate & ./<120 roposing the Reaction 7echanism 1. Elementary steps must add up to the overall e)uation ". Elementary steps must be physically reasonable 9as much as possibleunimolecular=bimolecular: 2. 7echanism must correlate with the rate law 7echanism with 4low $nitial 4tep 91: <1"9g: * 3"9g: <1"39g: * 39g: 9slow: 9": <1"9g: * 39g: <1"39g: 9fast: rate law of reaction: rate & ./<1"0/3"0 a: 1verall Reaction: "<1"9g: * 3"9g: "<1"39g: b: 7olecularity of each step: 91: !imolecular 9": !imolecular c: Rate ,aw for each step:

rate" & ." /<120/<10 rate & /<10"/1"0

EQUILIBRIUM rate of forward and reverse reactions are e)ual dynamic at the molecular level > we observe no further net ratefwd & raterev Kfwd/<"160e) & Krev/<1"0"e)

E)uilibrium +onstant- K a number e)ual to a particular ratio of e)uilibrium concentrations of product and reactant at a particular temperature magnitude of K is an indicator of extent of
//alyssaboller

Chemistry 3 First Quarter

reaction at a given temperature 1. 4mall K very little product as it reaches e)uilibrium ?no reaction@ ". ,arge K reaches e)uilibrium with very little reactant ?goes to completion@ 2. $ntermediate K significant amounts of reactant and products are present at e)uilibriumA ,aw of +hemical E)uilibrium at a given temperature- a chemical system reaches a state in which a particular ratio of reactant and product concentrations has a constant value for a particular system and temperaturesame e)uilibrium state is attained regardless of how the reaction is run. Reaction Buotient- B B is a ratio made up of product concentration terms multiplied together and divided by reactant concentration terms multiplied together- with each terms raised to the power of its stoichiometric coefficient in the balanced e)uation. !ased on concentration of reactants and products 9B+: 5he numerical value of B + changes during the reaction 7onitoring B tells whether the system has reached e)uilibrium 3or a reaction aA * b! c+ * d#-

more reactions- the overall reaction )uotient is the product of the reaction )uotients for the steps Boverall & B1 x B" x Bn Koverall & K1 x K" x Kn Comogenous D Ceterogenous E)uilibrium 1. Comogenous > same phase ". Ceterogenous > different phases 8$n writing B+- we do not include solids and li)uids because their concentrations are constant at a given temperature. Relation between K+ and K 3rom the $deal (as E)uation- we can relate the concentration and pressure of a gas: E & nR5 8pressure is directly proportional to molar concentration Bc & BpR5 Kp & Kc 9R5:Fngas 8Fngas & nproducts% nreactants

7anipulating E)uilibrium ,aws 1. +hanging the #irection of E)uilibrium reversing the reaction: use the reciprocal of the given K. ". 7ultiplying the +oefficient by a 3actor multiplying the coefficient: raise the given K by the multiplied value Reaction #irection: +omparing B and K e)ual at e)uilibrium K: e)uilibrium constant

3orms of B and K written as B+ and K+ because both are based on concentrations if an overall reaction is the sum of two or

specific at a particular temperature B: reaction )uotient changes during the reaction

//alyssaboller

Chemistry 3 First Quarter

since the value changes- can be G- H- or & to K 1. BHK reactants G products proceed toward the product side ". B G K products G reactants proceed toward the reactant side 2. B & K e)uilibrium

SIMPLIFYING ASSUMPTIONS FOR FINDING AN UNKNOWN QUANTITY $n general- a reaction has a relatively small K and a relatively large initial reactant concentration- the concentration change 9x: can often be neglected without introducing significant error. /reactant0initial % x & /reactant0e)uilibrium xO' /reactant0initial O /reactant0e)uilibrium JP Rule: if the assumption results a change 9error: in concentration that is less than JP- the error is not significant and the assumption is Qustified. Example: hosgene is a potent chemical warfare agent that is now outlawed by international agreement. $t decomposes by the reaction: +1+l"9g: +19g: * +l"9g: Kc & I.2 x 1' %6

ICE TABLE Example: 3or the reaction +19g: * C"19g: +1"9g: * C"9g: the value of the e)uilibrium constant is 1.I6J at a given temperature. We place '.J''ml +1 and '.J'' mol C"1 in a 1.''%, container at this temperature- and allow the reaction to reach e)uilibrium. What will be the e)uilibrium concentration of all the substances presentK
/+10 $nitial +hange
E)uilibrium

/C"10 '.J7 %x '.J%x

/+1"0 ' *x x

/C"0 ' *x x

'.J7 %x '.J%x

+alculate /+1+l"0- /+10 D /+l"0 when the reaction is at e)uilibrium in a 1'%, flas.. a. J.'' mol +1+l" +1+l" $ + E '.J7 %x '.J> x +1 ' *x x +l" ' *x x

Kc & 1.I6J &

&

x & 1.I6J 9x > x * '."J': ' & '.I6J x" > 1.I6Jx * '.6L1"J x& & 1.IMJ6 or '."INMI /+10 & '.J > x & '."1" 7 /C"10 & '."1" 7 /+1"0 & '."II 7 /C"0 & '."II 7
//alyssaboller

"

"

Assume x is very small that '.J'' 7 > x O '.J'' 7 therefore- x & ".' x 1'%" /+10 & /+l"0 & x & ".' x 1'%" 7 /+1+l"0 & '.J'' > x & '.6I 7

Chemistry 3 First Quarter

+CE+K:

When Sngas & ': change in pressure has no effect on the e)uilibrium condition

&G 6P error &G assumption is Qustified LE CHATELIER'S PRINCIPLE 4tates that if a system at e)uilibrium is disturbedthe e)uilibrium will shift to minimiRe disturbing influence $ntroduce ?disturbance@ by changing the concentration of reactants and=or products pressure or volume temperature +hanging +oncentration Adding reactant or product: e)uilibrium will shift to consume the added substances Removing reactant or product: e)uilibrium will shift to form the substances removed +hanging ressure and Eolume 9gaseous: $ncrease in external pressure will lead to decrease in volume and increase in gas pressure 5o counter balance this- the system shifts to the direction with less moles of gas 9higher volume D lower pressure:. #ecrease in external pressure will lead to increase in volume and decrease in gas pressure 5o counter balance this- the system shifts to the direction with more moles of gas Adding inert gas or gas not part of the e)uilibrium will only affect the total pressure but the partial of the reacting species are all unchanged As a result- the added gas has no effect in the e)uilibrium condition

+hanging 5emperature Endothermic > absorb heat 9*SC: reactants * heat product Exothermic > release heat 9%SC: reactants products * heat Raising the temperature shifts the e)uilibrium to the direction of the endothermic process ,owering the temperature shifts the e)uilibrium to the direction of the exothermic process Addition of +atalyst speeds up the rate of forward and reverse reactions but does not affect e)uilibrium condition Exercise: +onsider the following hypothetical e)uilibrium: A9g: "!9g: SC & JI.' .T #etermine the direction of shift if: 1. Add A9g: K roduct ". Remove "!9g:K roduct 2. $ncrease total by adding Ar9g:K <one 6. $ncrease the volumeK roduct J. #ecrease the temperatureK Reactant L. Adding catalystK <one LE CHATELIER'S PRINCIPLE: Q AND K

Bc & K+ at e)uilibrium At a given 5- the value of K+ does not change with a change in concentration

ressure and Eolume affects concentration increase in pressure & increase in concentration increase in volume & decrease in concentration

//alyssaboller

Chemistry 3 First Quarter

D E does not affect the value of K+

5emperature Endothermic 9SC G ': reactant * heat product Exothermic 9SC H ': reactant product * heat if we start with a system at e)uilibrium- Bc & Kc. $ncrease the temperature and the system responds by decomposing the elements whose side heat is on. 1ther side absorbs the added heat. 5he denominator of Bc becomes larger and the numerator smaller- so the system reaches a new e)uilibrium position at a smaller ratio of concentration termsthat is- lower than K+. $ncrease in 5 & increase in K+ 9with *SC reaction: $ncrease in 5 & decrease in K+ 9with %SC reaction B & increase in product concentration = decrease in reaction concentration: Knew H Korig

//alyssaboller