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Chapter IV - Experimental Methods
Chapter IV - Experimental Methods
Chapter IV - Experimental Methods
Objectives
➢ To know which experimental method you have to select for the studied reaction based on
chemical or physical properties of the reaction reagents or products.
➢ To give ideas about the common lab methods for chemical measurement (volumetry, pH-
metry, ..) or physical ones: spectrophotometry, polarimetry, conductimetry,
➢ To know what are continuous and discontinues methods and how we stop reaction for
discontinues analyses
➢ To know how to analyse the experimental results for the selected experimental method and
how to correlate the experimental results to the concentrations of the different reactants
present in the reaction medium: Reactants, products or both.
Pr. Iyad Karamé
The kinetic study is an experimental study: rate law is determined experimentally
➢ The measurement of the reaction progress requires the direct or indirect determination of the
concentration of one or more of the chemical species taking part in the reaction
➢ This measurement must be repeated at different reaction time in order to be able "to follow" the
evolution of the reaction in function of time.
➢ To determine the composition of the system during the reaction; we can analyse the chemicals in a
quantitative fashion or follow the reaction by measuring the variation of a physical property which
depends on the composition of the system.
➢ Rate law is a function of reagent concentration, or reaction composition
➢ Sometimes the analysis does not allow us to analyse directly the concentration of
reactants and products but physical properties allowing us to determine the
concentration
➢ Scientist has to be able to transform the integrated rate law to a function of time of:
✓ The property of at least one reactant
✓ The property of at least one product
✓ The property of the reaction mixture: reactants & products
Methods classification
We must keep the temperature T constant using thermostat
➢ A- Chemical: volumetric dosing-Titration, pH-metry
➢ B- Physical by measuring physical properties: pressure, electrical conductivity,
Absorbance, rotation angle for chiral species etc…)
❑ A’- Discontinues: Stopping reaction for analyzing & sampling (taking samples)
❑ B’- Continues: In-situ = direct and continue analysis, no need to stope reaction
➢ Dilution :
✓ Catalyst poisoning
2P0
PA= f (Pt, P0)= ?? PA0 =
3
𝟏 𝟏 𝑹𝑻 𝑹𝑻 P𝐴0
Order 2: - = 𝟐𝒌𝒕 ⇒ − = 𝟐𝒌𝒕 Order 1: 𝐿𝑛 = 2𝑘𝑡
[𝑨] [𝑨]𝟎 𝑷𝑨 𝑷𝑨𝟎 P𝐴
Kinetic study by pressure variation measurement
Of course the measured pressure is the total pressure of gaseous reagents
2 2 4
PA,t= P0 - 2X = P0 - 2(P0 - Pt)= 2Pt - P0
3 3 3
2
P∞= 2X. when PH2= 0 => P∞= 2X= P0
3
Pt=P0 – X
then X= P0 – Pt
2
P0
3
Order 1: 𝐿𝑛 4 = 2𝑘𝑡 Order 2:
2Pt − 3P0 𝑹𝑻 𝑹𝑻 𝟏 𝟏 𝟐𝒌𝒕
2P0 − = 𝟐𝒌𝒕 ⇒ − =
=> 𝐿𝑛 = 2𝑘𝑡 𝑷𝑨 𝑷𝑨𝟎 6Pt − 4P0 2P0𝟎 𝟑𝑹𝑻
6Pt − 4P0
Kinetic study by pressure variation measurement
Of course the measured pressure is the total pressure of gaseous reagents
2 2 4
PA,t= P0 - 2X = P0 - 2(P0 - Pt)= 2Pt - P0 𝟒
3 3 3 PA,t= 2Pt - P0= 2 Pt- 2P∞
𝟑
2
P∞= 2X. when PH2= 0 => P∞= 2X= P0
3
PA,0= P∞ Pt=P0 – X
then X= P0 – Pt
2
P0
3
Order 1: 𝐿𝑛 4 = 2𝑘𝑡
2Pt − 3P0
P∞
=> 𝐿𝑛 = 2𝑘𝑡
2Pt − 2P∞
Kinetic study by pressure variation measurement
Of course the measured pressure is the total pressure of gaseous reagents
2 2 4
PA,t= P0 - 2X = P0 - 2(P0 - Pt)= 2Pt - P0
3 3 3
2 Pt=P0 – X
P∞= 2X. when PH2= 0 => P∞= 2X= P0
3 then X= P0 – Pt
𝟒
PA,t= 2Pt - P= 2 Pt- 2P∞
𝟑 0
PA,0= P∞ Order 2:
P∞ 𝑹𝑻 𝑹𝑻 𝟏 𝟏 𝟐𝒌𝒕
Order 1: 𝐿𝑛 = 2𝑘𝑡 − = 𝟐𝒌𝒕 ⇒ − =
2Pt − 2P∞ 𝑷𝑨 𝑷𝑨𝟎 2Pt − 2P∞ P∞ 𝑹𝑻
Kinetic study by spectrophotometry
t= 0 a b 0 0 A0= 0 b>>>a
t a -x b - 2x 2x x At=l.ε.x 𝐝𝐱
= k.b.(a – x)
𝐝𝐭
End; t=
0 b-2a 2a a A∞=l.ε.a
∞ 𝐋𝐧
𝐚
= 𝐤𝐛𝐭 order 1
𝐴∞ −𝐴𝑡 𝐚−𝐱
a- x=
l.ε
A∞ A∞
Ln = k′t Ln(A∞ −At ) = −k′t + LnA∞
Ln l.ε = k′t A∞ − At
A∞ − At
l.ε
=>motion of ions
• Scientist must transform the rate law as a function of the solution’s conductivity
Conductivity of a solution is proportional to the concentration X= Λ.[C]
Where: Λ is the molar conductivity , [C]: concentration of ionic components
Time CH3COOEt + HO- → CH3COO- + EtOH X
t= 0 a a 0 0 X0= Λ.a 𝟏 𝟏
+ = k.t
(𝐚− 𝐱) 𝐚
t a -x (a-x) x x Xt=Λ.(a-x) + Λ’.x
End; t= ∞ 0 0 a a X∞=Λ’.a 𝐚
=> - 1= k.a.t
(𝐚− 𝐱)
X0− X∞
Xt- X∞=Λ.(a-x) + Λ’.x - Λ’.a = (Λ- Λ’)(a-x) (Λ− Λ’) 1 k.a.t 1
=> = + X −X
X0- X∞=Λ.a - Λ’.a = (Λ- Λ’)a Xt− X∞ - 1= k.a.t X t− X ∞ X0− X∞ 0 ∞
(Λ− Λ’)
X0 − X𝑡
𝒙 (Λ− Λ’) X0 − X t
Or
(𝐚− 𝐱)
= k.a.t X0- Xt= Λ.a - Λ.(a-x) - Λ’.x = (Λ- Λ’).x Xt− X∞ = k.a.t =>
Xt− X∞
= k.a.t
(Λ− Λ’)
Pr. Iyad Karamé
Kinetic Study by Polarimetry
This experiment consist on a material's ability to rotate polarization of light (physical property of chiral
compounds)
Scientist must transform the rate law as a function of the rotation α
Rotation coefficient of a solution is proportional to the concentration α= αs . l .[C]
Where: αs is the specific rotation of a chiral compound (intensive property)
l is length of the tube, [C] is the concentration of each chiral component
𝐝𝐱
Time Sucrose + H2O → Glucose (D) + Fructose (L) α = k.(a – x)(b – x)
𝐝𝐭
t= 0 a b 0 0 α0= δ.a (δ= cte.)
t a -x (b-x) x x αt=δ.(a-x) +δ’.x b>>>a
𝐝𝐱
End; t= ∞ 0 (b-a) a a α∞=δ’.a = k.b.(a – x)
𝐝𝐭
𝐚
𝐋𝐧 = 𝐤𝐛𝐭 order 1
𝐚−𝐱
αt - α∞ =δ.(a-x) +δ’.x - δ’.a= (a-x)(δ - δ’) α0- α∞ =δ.a +δ’.a= a(δ - δ’)
α0− α∞
⇒ 𝐋𝐧 = 𝐤𝐛𝐭
αt − α∞
Pr. Iyad Karamé