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Chemical Ideas 10.3. The Effect of Concentration on Rate. rate Listen: [ r ā t ] n. A quantity measured with respect to another measured quantity. speed = rate of change of distance . inflation = rate of change of prices. m/s. % /year.
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Chemical Ideas 10.3 The Effect of Concentration on Rate
rateListen: [ rāt ]n. A quantity measured with respect to another measured quantity. speed = rate of change of distance inflation = rate of change of prices m/s %/year when taking about rate you MUST be clear about units being used
rate at which products are converted to reactants rate of reaction
0.0001 mol O2 formed 0.0002 mol H2O formed 0.0002 mol H2O2 used up EACH SECOND!!!
change of property time Measuring the rate of a reaction. measure the change in amount of a reactant or product in a certain time • Decide on a property of reactant or product that you can measure. • Measure the change in property over a certain time • Find the rate
This graph shows us that rate is directly proportional to the concentration of hydrogen peroxide rate = constant x [H2O2(aq)] rate [H2O2(aq)]
The concentration of the enzyme catalase also affects the rate of the reaction … rate = constant x [catalase] We can combine the two equations to get … rate = constant x [H2O2(aq)] x [catalase] rate = k [H2O2(aq)] [catalase]
rate = k [H2O2(aq)] [catalase] • This is the rate equation for the reaction • the constant k is called the rate constant • k varies with temperature, therefore you must always state the temperature at which measurements are made.
Order of a Reaction • For a reaction in which A & B are reactants … • A + B products • The general rate equation is… • rate = k [A]m [B]n • m and n are powers to which the concentration must be raised. usually have values of 0, 1 or 2. • m & n are called the order of the reaction
decomposition of hydrogen peroxide rate = k [H2O2(aq)] [catalase] • The reaction is first order with respect to H2O2 • The reaction is also first order with respect to catalase. • The overall order of a reaction is given by (m + n). • the reaction is overall second order
For the reaction 2Br (g) Br2(g) • Rate equation is • rate = k [Br]2 • S2O82-(aq) + 2I- (aq) SO42-(aq)+ I2 (aq) • rate =k [S2O82-(aq) ] [I- (aq) ] you cannot predict the rate equation for a reaction from it’s balanced equation
BrO3-(aq) + 5Br-(aq) + 6H+ (aq) 5H2O(l)+ 3Br2 (aq) rate =k [BrO3-] [Br-] [H+]2 you cannot predict the rate equation for a reaction from it’s balanced equation
Chemical Ideas 10.3 (again) Knowing how concentration affects rate can tell us something about the way reactions occur.
Remember … The rate of any reaction can be expressed in terms of the concentrations of its reactants rate = k [A]x [B]y [C]z x,y & z are the order of the reaction with respect to that reaction. If they =1 the number is not shown
decomposition of hydrogen peroxide rate = k [H2O2(aq)] [catalase] • The reaction is first order with respect to H2O2 • The reaction is also first order with respect to catalase. • The overall order of a reaction is given by (m + n). • the reaction is overall second order
half-lives (t ½ ) Reactions which are first order will show a curve that is identical to radioactive decay! Time taken for half of a reactant to get used up in the reaction
zero order & second order reactions do not have this feature For a first order reaction the half-life is always constant no matter what the starting amount!
Finding the Order of a Reaction you cannot predict the rate equation for a reaction from it’s balanced equation • To find out the order of a reaction it is necessary to carry out practical experiments. • The data can then be used to determine the order of the reaction.
Progress Curve Method • Rate is calculated by drawing tangents to the curve at various points • Can then find the order with respect to a reactant/product • tedious & inaccurate (unless using a PC?)
Initial Rates Method – drawing tangents • most used • Several experimental runs are completed (as in activity EP6.3). • Initial rate is calculated by drawing tangents at the origin. • We then plot initial rate against concentration
producing graphs first order zero order rate rate [A] [A] second order second order rate rate [A] [A]2
Initial Rates Method – reciprocal of time • Measuring how long to produce a small fixed amount of one of the products. • Time taken is called the reaction time. • Rate is high – reaction time small • Rate low – reaction time large. • Average rate 1/t . • Graph of 1/tagainst concentration.
half-lives method • You can use the progress curve to determine half-lives for the reaction. • If they are constant then the reaction is first order.
rate equations & rate mechanisms when we know the rate equation we can link it to the reaction mechanism. We can then work out the rate determining step.
CH3 CH3 C Br CH3 + OH- first order w.r.t. (CH3)3CBr CH3 zero order w.r.t. OH- CH3 C OH + Br- CH3 rate = k[(CH3)3CBr]
CH3 CH3 CH3 CH3 CH3 C+ C+ CH3 C Br CH3 CH3 CH3 CH3 CH3 C OH CH3 step one Br- + slow step two OH- + Ξfast
mechanism of enzyme catalysed reactions … • when the substrate concentration is low for the reaction • rate = k[E][S] ([E] is concentration of enzyme) • we can deduce from this that the rate determining step involves one enzyme molecule & one substrate molecule. • Following steps are faster. • Substrate concentration high then • rate = k [E]
WHY? – why are some steps slow & others fast? • One reason = different steps have different activation enthalpies. • Large activation enthalpy, only a small number of molecules pass over it each second so rate of reaction is slow. • Small activation enthalpy, greater proportion of molecules can pass each second, hence a faster rate.