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.

➢ The "follow-up of the concentration change in a reaction” is a delicate operation because it is

necessary to have a good precision in the time determination. We must keep the temperature
➢ The precise definition of initial time "time zero" is also delicate. T constant using thermostat

➢ 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

➢ To determine the concentration of the reagent we need an analysis method

➢ 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

❖ A”- Destructive (only one measurement): sample is destroyed like in MS analysis

❖ B”- Non-destructive (here you can recover the sample): NMR, polarimetry,
spectrophotometry..
 ❑ Discontinues Methods ❑Continues Methods
Stopping reaction for analyzing & Direct and continue analysis,
Sampling (taking samples) No need to stope reaction

Volumetric dosing Polarimetry

Spectrophotometry Conductimetry
NMR Pressure variation measurement
GC-MS, LC-MS In-situ Infra-red
….. …
 Stopping reaction

Needed when analysis method is discontinued

➢ Dilution :

➢ Thermal curing : cooling

➢ Chemical blocking (quenching) :

✓ Catalyst poisoning

✓ One reactant blocking or elimination

 Kinetic study by pressure variation measurement
Of course the measured pressure is the total pressure of gaseous reagents in closed reactor

2A (g) + B (g) → 2C (g) nt Pt

3n0 RT
t=0 2n0 n0 0 3n0 P0=
V
(3n0 −x)RT
t 2n0- 2x n0 - x 2x 3n0-x Pt= V
2n0 RT
t= ∞ 0 0 2n0 2n0 P∞= V

2P0
PA= f (Pt, P0)= ?? PA0 =
3

RT 2n0 RT 2xRT (3n0 −x)RT 3n RT xRT xRT

PA= (2n0-2x) = − Pt= = 0 - = P0-
V V V V V V V
2P0 4P0 xRT
=> PA = – 2(P0-Pt) = 2Pt- => P0 -Pt=
V
3 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

2A (g) + B (g) → 2C (g).

t=0 2P0/3 P0/3 0 Ptotal= P0

t 2P0/3 - 2X P0/3 – X 2X Pt=P0– X

t= ∞ 0 0 2P0/3 P∞= 2P0/3

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

2A (g) + B (g) → 2C (g).

t=0 2P0/3 P0/3 0 Ptotal= P0

t 2P0/3 - 2X P0/3 – X 2X Pt=P0– X

t= ∞ 0 0 2P0/3 P∞= 2P0/3

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

2A (g) + B (g) → 2C (g).

t=0 2P0/3 P0/3 0 Ptotal= P0

t 2P0/3 - 2X P0/3 – X 2X Pt=P0– X

t= ∞ 0 0 2P0/3 P∞= 2P0/3

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

This method consists of a material's ability to absorb light

The method used here can be used only for reaction where at least one component of
the reaction medium is light absorbent, Scientist must check the wavelength (λ) at
which the component absorbs light in UV/visible and the lamps power of his
spectrophotometer
Scientist has:
• To transform the rate law as a function of the absorbance of the absorbent component
• To stop reaction

Pr. Iyad Karamé

 Kinetic study by spectrophotometry

Where: l is the length of tube of Spectrophotometer,

Absorbance A=l.ε.[C] ε [C]: extinction coefficient of the component absorbent and its
concentration
𝐝𝐱
= k.(a – x)(b – 2x)
Time S2O82- + 2I − → 2SO42− + I2 A 𝐝𝐭

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

Pr. Iyad Karamé

 Kinetic study by conductimetry Ex: second order reaction
This method consists of a material's ability to allow the transport of an electric charge (physical property)

=>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