Tutorial on Reactivity Series vs Electrochemical

Series.

Prepared by
Lawrence Kok
http://lawrencekok.blogspot.com
 Chemical Properties Group 1 Reactivity Gp 1
shell

Li 2.1

Na 2.8.1

Click here video potassium in water

K 2.8.8.1

2.8.8.18.1
Rb
Group 1 (Alkali Metal)

Chemical reaction Oxidizing agent using potassium chlorate

Size increase
Reaction with water Reaction with oxygen Reaction with halogen
lose electron easily
electropositive 2Li + 2H2O -> 2LiOH + H2 4Li + O2 -> 2Li2O 2Li + CI2 -> 2LiCI
2Na + 2H2O -> 2NaOH + H2 4Na + O2 -> 2Na2O 2Na + CI2 -> 2NaCI
Reactivity increase 2K + 2H2O -> 2KOH + H2 4K + O2 -> 2K2O 2K + CI2 -> 2KCI

Kept in paraffin oil

Click here video sodium in water

Lithium – move slowly surface water – red flame

Strong reducing agent Sodium – move fast, hissing sound – yellow flame Similar chemical property but diff reactivity
Reduce H+ ion to H2 gas Potassium – move fast, ignite - lilac flame Lithium –burn slowly , red flame
(losing e to H+) Turn red litmus blue- produce hydrogen gas Sodium – burn brightly, yellow flame
Solution of metal hydroxide/alkaline produced Potassium –burn very brightly, lilac flame
 Reactivity Series Reactive metal How fast rxn happen? (Kinetics)

• Metal arranged according to their ability to lose electron - form +ve ions
• Measure tendency of metals in losing electrons (Undergo oxidation)
• Metals – lose electrons – form electropositive ions – Oxidation Process

Reactivity series
Metals with water, acids, oxygen

Displacement rxn (H atom from H2O/HCI)

Reactive metal displace H atom from water
2K + 2H2O → 2KOH + H2 Click here to view Flinn Scientific
Ca + 2H2O → Ca(OH)2 + H2

Less reactive metal displace H atom from acid

Reactivity series
Non metal, Hydrogen and Carbon
Reactivity series
Mg + 2HCI → MgCI2 + H2
Zn + H2SO4 → ZnSO4 + H2
Unreactive metal – No rxn with water /acid
Au + HCI →
Click here AI/CuCI3 displacement
Displacement rxn (REDOX reaction)
Reactive metal displace less reactive metal from its sol

Displacement rxn (O atom from less reactive)

Reactive metal displace O from less reactive metal
2Al + Fe2O3 → Al2O3 + 2Fe
lithium Zn + PbO → ZnO + Pb
Click here microscale Fe reduction
Displacement rxn (O atom from less reactive)
Reactive non metal displace O from less reactive metal
C + 2Fe2O3→ 3CO2 + 4Fe
H2 + CuO→ H2O + Cu

Displacement rxn (less reactive ions)

Reactive metal displace less reactive ions from its salt
Zn + CuSO4 → ZnSO4 + Cu
2Al + 3CuCI2 → 2AlCI3 + 3Cu
Click here Iron extraction (Thermite)
 Electrochemical Series Thermodynamics measurement

STANDARD Reduction potential – H2 as std

WEAK STRONG
Oxidizing Agent Oxidized sp ↔ Reduced sp E /V
θ Reducing Agent
Li+ + e- ↔ Li -3.04
K +
+ e- ↔ K -2.93
Ca2+ + 2e- ↔ Ca -2.87
Na+ + e- ↔ Na -2.71
TOP left
TOP left Mg + 2e-
2+
↔ Mg -2.37 TOP
TOP right
right
•• Low Low ↓ ↓ tendency
tendency gaingain e
e -ve •• High
•• Li
Al 3+
+ 3e- ↔ AI reduction
-1.66 High ↑ ↑ tendency
tendency lose
lose e
e
e→
+
Li +
+
+e → LiLi Mn2+ + 2e- ↔ Mn -1.19 •• Li → Li +
+ +e
Li → Li + e
•• E θ Li= - 3.04V
θ potential
E Li= - 3.04V H2O + e- ↔ H2+OH- -0.83 •• E θ
Eθ Li = +3.04V
Li = +3.04V
•• WEAK
WEAK oxidizing
oxidizing Agent
Agent •• STRONG
•• Red Zn2+ + 2e- ↔ Zn -0.76 STRONG reducing
reducing Agent
Agent
Red NOTNOT favourable
favourable ••Oxi favourable (E θ =+ve)
θ
(E Fe + 2e-
2+
↔ Fe -0.45 Oxi favourable (E =+ve)
(Eθ =-ve)
θ
=-ve)
Ni + 2e-
2+
↔ Ni -0.26
Sn2+ + 2e- ↔ Sn Compared to -0.14
Pb + 2e-
2+
↔ Pb H2 as std -0.13
H +
+ e- ↔ 1/2H2 0.00
Cu2+ + e- ↔ Cu+ +0.15
SO4 + 4H + 2e- ↔ H2SO3 + H2O
2- +
+0.17
Cu2+ + 2e- ↔ Cu +0.34
1/2O2 + H2O +2e- ↔ 2OH- +0.40
BOTTOM
BOTTOM left left
•• High
Cu+ + e- ↔ Cu +0.52 BOTTOM
BOTTOM right
right
High ↑ ↑ tendency
tendency gain
gain e
e ↔ I- •• Low ↓
1/2I + e- +0.54 Low ↓ tendency
tendency lose
lose e
e
•• F F22 + 2e →
+ 2e → 2F
- 2
2F- +ve •• F F → → 1/2F
1/2F22 +
+e
--
•• E θ F = +2.87V
θ Fe3+ + e- ↔ Fe2+ +0.77 e
E F22= +2.87V reduction
↔ Ag •• E = -- 2.87V
θ
Ag+ + e- +0.80 Eθ F F22 = 2.87V
•• STRONG oxidizing
STRONG oxidizing Agent Agent potential
••Red
1/2Br2 + e- ↔ Br- +1.07 •• WEAK
WEAK reducing Agent
reducing Agent
favourable
Red favourable
1/2O2 + 2H+ +2e- ↔ H2O +1.23 ••Oxi
Oxi NOTNOT favourable
favourable (E
(Eθ =-ve)
θ
=-ve)
(E
(Eθ =+ve)
θ
=+ve)
Cr2O72-+14H+ +6e- ↔ 2Cr3+ +7H2O +1.33
1/2CI2 + e- ↔ CI- +1.36
MnO4- + 8H+ + 5e- ↔ Mn2+ + 4H2O +1.51
Strong WEAK
1/2F2 + e- ↔ F +2.87
Oxidizing Agent Reducing Agent
E cell/Cell Potential = EMF in volt
θ

EMF when half cell connect to SHE std condition

Std potential written as std reduction potential
 Reactivity vs Electrochemical Series
Reactivity Series Electrochemical Series

Reactivity – Kinetics Electrochemical Series - Thermodynamics measurement

↓ ↓
Eθ value give – energetics feasibility of rxn- not rate/kinetics
How fast/metal with water and acid
↓
↓ Rxn may be feasible,
Due to low Ea – easier to react but to slow to happen/no observable sign – Ea too high
↓ ↓
Potassium + water = faster/reactive Measurement of voltage/potential using Std H2 Electrode
Lithium + water = slower/less reactive

Oxidized sp ↔ Reduced sp Eθ/V

Li+ + e- ↔ Li -3.04
lithium Li
K+ + e- ↔ K -2.93
Ca2+ + 2e- ↔ Ca -2.87
Na+ + e- ↔ Na -2.71
Mg 2+ + 2e- ↔ Mg -2.37
Al3+ + 3e- ↔ AI -1.66
Zn2+ + 2e- ↔ Zn -0.76
Fe2+ + 2e- ↔ Fe -0.45
Ni2+ + 2e- ↔ Ni -0.26
Pb2+ + 2e- ↔ Pb -0.13
Cu2+ + 2e- ↔ Cu +0.34
Ag+ + e- ↔ Ag +0.80

Potassium > Sodium > Lithium Lithium > Potassium > Sodium

Strong Correlation but may not be the same

↓
Li to Li ion more thermodynamically favourable than K to K + ion
+

↓
K more reactive than Li in water/acid – due to kinetics factor
Electrochemical Series - Thermodynamics measurement Electrochemical Series
M(s) → M+(g) + e
STD Oxidation potential
3 Steps rxn:
M (s) → M (g) ∆H = enthalpy of atomization Reduced sp ↔ Oxidized sp Eθ/V
M (g) → M+ (g) ∆H = enthalpy of ionization Li ↔ Li+ + e +3.04
K ↔ K+ + e +2.93
M+(g) → M+(aq) ∆H = enthalpy of hydration
Na ↔ Na+ + e +2.71

Lithium – Size smaller Potassium– Size bigger

↓ ↓
Easily hydrated → - ∆H favourable Diff hydrated → +∆H non favourable
↓ ↓
IE High – strong NC due to small size IE Low – weak NC due to large size

K
Li Na

Li → Li+(g) Na → Na+(g)
K → K+(g)

∆HI = +519 ∆Hhyd = - 499 ∆HI = +494 ∆Hhyd = - 390

∆HI = +418 ∆Hhyd = - 305

Li(s) → Li (g) Na(s) → Na(g) Na+(g) → Na+(aq)

K (s) → K (g) K +
(g) →K+
(aq)
Li+(g) → Li+(aq)

∆Ha = +161 ∆Ha = +90 ∆Ha = +108 Na(s) → Na+(aq) ∆H = +212

Li(s) → Li + (aq) ∆H = +181 K(s) → K +(aq) ∆H = +203
Li(s) K (s) Na (s)

Lithium – least ∆H change Potassium – High ∆H change Sodium – Highest ∆H change

- Most energetically favourable - Less energetically favourable - Least energetically favourable
-∆H = spontaneous/favourable -∆H = spontaneous/favourable +∆H = NON spontaneous/favourable

-∆H = spontaneous/favourable -∆H = spontaneous/favourable +∆H = NON spontaneous/favourable

↓ ↓ ↓
Li → Li + e
+
+Eθ K → K+ + e +Eθ Na → Na + + e +Eθ
 Reactivity vs Electrochemical Series
STD Oxidation
Reactivity Series Electrochemical Series
potential
vs Reduced sp ↔ Oxidized sp Eθ/V
Potassium K Li ↔ Li+ + e +3.04
Sodium Na K ↔ K+ + e +2.93
Lithium Li Na ↔ Na+ + e +2.71

Potassium > Sodium > Lithium Lithium > Potassium > Sodium

Lithium is above Potassium in electrochemical series

↓
Lithium is below Potassium in Reactivity Series
↓
Due to kinetics factors/activation energy, Rxn is slower

Li → Li+(g) Na → Na+(g)
K → K+(g)

∆HI = +519 ∆Hhyd = - 499 ∆HI = +494 ∆Hhyd = - 390

∆HI = +418 ∆Hhyd = - 305

Li(s) → Li (g) Na(s) → Na(g) Na+(g) → Na+(aq)

K (s) → K (g) K +
(g) →K +
(aq)
Li+(g) → Li+(aq)

∆Ha = +161 ∆Ha = +90 ∆Ha = +108 Na(s) → Na+(aq) ∆H = +212

Li(s) → Li + (aq) ∆H = +181 K(s) → K +(aq) ∆H = +203
Li(s) K (s) Na (s)

Lithium – least ∆H change Potassium – High ∆H change Sodium – Highest ∆H change

- Most energetically favourable - Less energetically favourable - Least energetically favourable
-∆H = spontaneous/favourable -∆H = spontaneous/favourable +∆H = NON spontaneous/favourable

-∆H = spontaneous/favourable -∆H = spontaneous/favourable +∆H = NON spontaneous/favourable

↓ ↓ ↓
Li → Li + e
+
+Eθ K → K+ + e +Eθ Na → Na + + e +Eθ
 Acknowledgements
Thanks to source of pictures and video used in this presentation

Thanks to Creative Commons for excellent contribution on licenses

http://creativecommons.org/licenses/

Prepared by Lawrence Kok

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http://lawrencekok.blogspot.com