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Order of reaction
•Order of a reaction refers to the power dependence of the rate
of concentration of each reactant.
•Order is an experimentally determined parameter.
•For first order reaction , rate is dependant on the
concentration of a single species.
Determination of reaction order
❖Exact order of a reaction can be determined experimentally.
❖The methods to determine reaction order are:
•Graphical Method
•Substitution Method
•Half life Method
•Van’t Hoff differential Method
•Ostwald’s isolation Method
Graphical Method
▪In presence of single reactant.
▪Rate versus concentration graph:
•‘Log(a-x)’ vs ‘t’ : straight line = first order reaction.
•‘1/(a-x)’ vs ‘t’ : straight line = second order reaction.
•‘1/(a-x)^2’ vs ‘t’ : straight line = third order reaction.
Substitution Method
•Hit and trial method.
•Integrated rate law method.
•Concentration and time will be given.
•The value of k is determined .
•If the value of k is constant ,the used
equation gives the order of reaction.
Half-life method
• Only used when the rate law involve one concentration
term.
• t(1/2) ∞ a1-n
t(1/2) = k’a1-n
log t(1/2) = log k’ + (1-n)loga
• Graph can be drawn where the slope is (1-n) ,
n = order of reaction.
• If different concentrations are given the ratio of half life
is taken.
,
• By taking logs and rearranging,
Van’t Hoff differential method
•The rate of a reaction varies as the ‘n’th power of the
concentration of the reactant , where,
n= reaction order.
• Thus, for two different initial concentrations C1 and C2,
equations can be written in the form:
,
• Taking logarithm and subtracting,
•Or , n = [log(-(dC1)/dt)-log((dC2)/dt)] ÷ [logC1 - log C2]
❑ nA Product
rate = k[A] ⁿ
dxldt = k[A] ⁿ
log(dxldt) = logk + nlogA
y = c + mx (Slope = n)
Ostwald’s isolation method
• Initial rate method.
• Initial rate of reaction is determined by varying the
concentration of the reactants while others are kept constant.
• For a reaction given by:
aA + bB → cC + dD
• Rate ∝ [A]x[B]y ⇒ Rate = k[A]x[B]y , where ,
• [A] and [B] are concentration of reactants .
• k is the constant.
• x and y are the partial reaction order.
• If [B] is kept constant,
• R(1) = k[A1]x
• R(2) = k[A2]x
• R(1) / R(2) = ( [A1]/[A2])x
Thank You..
Soniya . M . Sunil
B. Pharm
3rd year
Mar Dioscorus College of Pharmacy

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Determination of reaction order.

  • 1. Order of reaction •Order of a reaction refers to the power dependence of the rate of concentration of each reactant. •Order is an experimentally determined parameter. •For first order reaction , rate is dependant on the concentration of a single species.
  • 2. Determination of reaction order ❖Exact order of a reaction can be determined experimentally. ❖The methods to determine reaction order are: •Graphical Method •Substitution Method •Half life Method •Van’t Hoff differential Method •Ostwald’s isolation Method
  • 3. Graphical Method ▪In presence of single reactant. ▪Rate versus concentration graph: •‘Log(a-x)’ vs ‘t’ : straight line = first order reaction. •‘1/(a-x)’ vs ‘t’ : straight line = second order reaction. •‘1/(a-x)^2’ vs ‘t’ : straight line = third order reaction.
  • 4. Substitution Method •Hit and trial method. •Integrated rate law method. •Concentration and time will be given. •The value of k is determined . •If the value of k is constant ,the used equation gives the order of reaction.
  • 5. Half-life method • Only used when the rate law involve one concentration term. • t(1/2) ∞ a1-n t(1/2) = k’a1-n log t(1/2) = log k’ + (1-n)loga • Graph can be drawn where the slope is (1-n) , n = order of reaction. • If different concentrations are given the ratio of half life is taken. , • By taking logs and rearranging,
  • 6. Van’t Hoff differential method •The rate of a reaction varies as the ‘n’th power of the concentration of the reactant , where, n= reaction order. • Thus, for two different initial concentrations C1 and C2, equations can be written in the form: , • Taking logarithm and subtracting, •Or , n = [log(-(dC1)/dt)-log((dC2)/dt)] ÷ [logC1 - log C2] ❑ nA Product rate = k[A] ⁿ dxldt = k[A] ⁿ log(dxldt) = logk + nlogA y = c + mx (Slope = n)
  • 7. Ostwald’s isolation method • Initial rate method. • Initial rate of reaction is determined by varying the concentration of the reactants while others are kept constant. • For a reaction given by: aA + bB → cC + dD • Rate ∝ [A]x[B]y ⇒ Rate = k[A]x[B]y , where , • [A] and [B] are concentration of reactants . • k is the constant. • x and y are the partial reaction order. • If [B] is kept constant, • R(1) = k[A1]x • R(2) = k[A2]x • R(1) / R(2) = ( [A1]/[A2])x
  • 8. Thank You.. Soniya . M . Sunil B. Pharm 3rd year Mar Dioscorus College of Pharmacy