Cheatsheets for Important Chapters - Chemistry

Chapter - Electrochemistry

1. Electrochemical Cells:
For any electrode →Oxidation potential = −Reduction potential.

Ecell = Reduction potential of cathode –Reduction potential of anode.

Ecell = Reduction potential of cathode +Oxidation potential of anode.
Ecell is always a positive quantity for a spontaneous reaction; Anode will be electrode of low reduction potential and Cathode will be of high reduction potential.
E∘cell = SRP of cathode −SRP of anode. (SRP = Standard Reduction Potential)
The greater is the SRP value, the greater will be oxidising power.

2. Different types of Electrodes:

(i) Metal-metal ion electrode (M +n)

Mn+ + ne− → M (s)

(ii) Gas-ion Electrode Pt |H2 (P atm)|H+ (X M)

1
2
PH2
As reduction electrode , H+ (aq) + e− → 1 H2 (P atm), E = E∘ − 0.0591log +
2 [H ]

(iii) Oxidation-reduction electrode Pt∣∣Fe

2+ 3+
, Fe

3+ [Fe2+]
As reduction electrode, Fe + e− ⟶ Fe2+ E = E∘ − 0.0591 log
[Fe3+]

(iv) Metal-metal insoluble salt electrode e. g. , Ag∣∣AgCl, Cl−

As reduction electrode, AgCl (s) + e− ⟶ Ag (s) + Cl−.

ECl−|AgCl|Ag = E0Cl−|AgCl|Ag − 0.0591 log [Cl−]

3. Gibbs Free Energy Change:

ΔG = −nFEcell
4. Nernst Equation:

(Effect of concentration and temperature on emf of cell)

ΔG = ΔG ∘ + RTlnQ (where Q is reaction quotient)

ΔG ∘ = −RTlnKeq

Ecell = E∘cell − 2.303RT

nF
logQ

Ecell = E∘cell − 0.0591

n logQ [At 298 K]

At chemical equilibrium: ΔG = 0 ; Ecell = 0

nE0cell
logKeq = 0.0591

0.0591
E0cell = n logKeq

5. Concentration Cell:

A cell in which both the electrodes are made up of the same material.

For all concentration cell,

E∘cell = 0
(i) Electrolyte Concentration Cell:

e.g., Zn(s) ∣∣Zn2+(c1) ∥∥Zn2+(c2) ∣∣Zn(s) E = 0.0591 C

2
log C2
1

(ii) Electrode Concentration Cell:

∣ ∣ ∣
e.g., Pt,H2(P1atm) ∣H+(1M) ∣H2(P2 atm) ∣Pt E = 0.0591 log ( )
P1
2 P2

6. Calculation of different Thermodynamics Function of Cell Reaction:

ΔG = −nFEcell

ΔS = −[ dG
dT
] (At constant pressure)
P

−[ dT ]
d(ΔG) d
ΔS = = nF( dt (Ecell))
P P

[ ]
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 [ ∂T ] =Temperature coefficient of emf of the cell.
∂E
P

E = a + bT + CT 2 + … + kT n−1

ΔH = nF [T( ∂T ) − E]
∂E
P

ΔCp of cell reaction:

dH
CP = dP

d
ΔC P = dT
(ΔH)

d 2Ecell
ΔC P = nFT
dT 2

7. Electrolysis:

K+,Ca+2,Na+,Mg+2,Al+3,Zn +2,Fe+2,H+,Cu +2,Ag+,Au +3

(i) >
Increasing order of deposition.

(ii) Similarly, the anion which is stronger reducing agent (low value of SRP) is liberated first at the Anode.

SO2− − − − − −
4 ,NO3 ,OH ,Cl ,Br ,I
>
Increasing order of deposition

8. Faraday's Law of Electrolysis:

(i) First Law:

w = Zq w = Zit = Electrochemical equivalent of substance.

(ii) Second Law:
W1 W2
W α E W
E
= constant =
E1 E2

W i×t× current efficiency factor

E
= 96500

Actual mass deposited

produced
Current efficiency = × 100
Theoretical mass deposited
produced

9. Conductance in Electrolytic Solutions:

1
(i) Conductance = Resistance

(ii) Specific conductance or conductivity:

(Reciprocal of specific resistance) κ = ρ 1 κ = specific conductance

specific conductance=conductance× al

(iii) Equivalent conductance:

κ×1000
λE = Normality unit : ohm−1cm2eq−1

(iv) Molar conductance:

λm = κ×1000
Molarity
unit : ohm−1cm2mole−1

10. Kohlrausch's Law:

Variation of λeq & λM of a solution with concentration:

(i) Strong electrolyte λcM = λ∞

M − b√c

(ii) For both strong and weak electrolytes:

λ∞ = n+λ∞ ∞
+ + n−λ where λ is the molar conductivity.

n+ = No. of cations obtained after dissociation per formula unit.

n=No. of anions obtained after dissociation per formula unit.
11. Application of Kohlrausch’s Law:

(i) Calculation of λ0m of weak electrolytes:

λoM(CH3COOH) = λ0M(CH3COONa) + λ0M(HCl) − λ0M(NaCl)

(ii) To calculate degree of dissociation of a weak electrolyte

λ m cα 2
α= ; Keq = (1−α)
λ0m

(iii) Solubility (S)of sparingly soluble salt & their Ksp

1000
λM = λoM = κ × solubility Ksp = S2

(iv) Ionic mobility: It is the distance travelled by the ion per second under the potential gradient of 1 volts per cm. Its unit is cm2s−1v−1.

(v) Absolute ionic mobility:

λoc α μc; λ0a ∝ μa

0 0 0 0
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λ0c = F × μ0c; λ0a = F × μ0a
Speed v
Ionic Mobitity μ = Potential gradient = V
l

(vi) Transport Number:

tc = [ μc+μa ], ta = [ μa+μc ]
μc μa

Where tc = Transport Number of cation & ta = Transport Number of anions.

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Chapter - Ionic Equilibrium

1. Acid and Base:

(i) Arrhenius Concept: Acid ionizes in water to give H3O+ ion while base ionizes to give OH− ion.

(ii) Bronsted-Lowry's Protonic Concept: Acid is H+ ion donor, and base is H+ ion acceptor.

(iii) HCl and chloride ion is a conjugate acid-base pair. If acid is weak, its conjugate base is strong and vice-versa.

(iv) A substance that can accept H+ ion as well as can donate H+ ion is called amphiprotic or amphoteric.

H3O+ ⇌ H2O ⇌ H+ + OH−

(v) A Bronsted-Lowry acid-based reaction is always favored in the direction from the stronger to the weaker acid/base combinations.
2. Lewis Concept:

(i) Lewis acid is an electron-pair acceptor.

(ii) Lewis base is an electron-pair donor.
(iii) All Lewis bases are Bronsted-Lowry bases, but all the Lewis acid are not Bronsted acids.
3. Ionic Product of Water:

Kw = [H3O+][OH] = 1 × 10−14 at 298 K

Kw is called an ionic product of water or autoionization or autoprotolysis constant.
4. Ionization of Acids and Bases:
(i) In a mixture of strong acids/bases:
ΣNV
[H+] = [H3O+] = ΣV
,[OH−] = ΣNV
ΣV

(ii) In a mixture of acid and base, resultant is

(a) acidic mixture if N1 V1 (acid) > N2 V2 (base)

N1 V1−N2 V2
[H+
3 O] = V1+V2

(b) basic mixture if N2 V2 (base) > N1 V1 (acid)

N2 V2−N1 V1
[OH−] =
V1+V2

(c) neutral mixture if N1 V1 (acid) = N2 V2 (base)

(iii) For conjugate acid-base pairs,

KaKb = Kw = 1 × 1014 at 25∘C

KaKb = Kw = 10−12 at 90∘C

Where Ka is the ionization constant of acid and Kb is the ionization constant of its conjugate base,

HA + H2O ⇌ H3O+ + A−, Ka

A− + H2O ⇌ HA + OH−,Kb
pKa + pKb = 14 = pKw
5. pH Scale:

pH = −log [H3O+]

pOH = −log[OH−]

pX = −log X

pH + pOH = pKw = 14

6. Ostwald Dilution Law:

According to Ostwald dilution law α ∝ √ dilution

At infinite dilution, ∝= 100%

For a weak acid by Ostwald dilution law
Cα 2
Ka = (1−α) ≈ Cα2

[H+] = √KaC, pH = 12 [pKa − logC]

[H+] = Cα

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and for a weak base:
Cα 2
Kb = ≈ Cα2 [OH−] = Cα
(1−α)

[OH−] = √KbC, pOH = 12 [pKb − logC]

Note: Ostwald dilution law is only applicable for weak electrolytes

7. Salt and Salt Hydrolysis:

Salt + Water ⇌ Acid + Base

In the above step, hydrolysis is an endothermic step whereas neutralization is an exothermic step.
Types of Salt:

(i) General
(ii) Acidic
(iii) Basic
(iv) Mixed
(v) Double

(vi) Complex
Types of General Salts:

(i) SA & SB

(ii) SA & WB

(iii) WA & SB

(iv) WA & WB

Types of salt Name of hydrolysis Nature of aqueous solution and pH

SA & SB - Neutral , pH = 7

SA & WB Cationic Acidic , pH < 7

WA & SB Anionic Basic , pH > 7

Ka > Kb Kb > Ka Ka = Kb
Hydrolysis Cationic-anionic Anionic-cationic Neutral hydrolysis
Nature Acidic Basic Neutral
pH pH < 7 pH > 7 pH = 7

For WA - WB types of salt:

Kw
Kh = lonization constant of weak acid or base

Summary:

h = √ Ch
Kw K
Type of salts Kh = lonisation constant of weak [H+] pH
SA & SB - - - 7
h = √K √ KwC×Ka 7 + 12 pKa + 12 logC
KW Kw
WA & SB Kh =
Ka a×C

√K w √
KW K Kw×C
SA & WB Kh = h= 7 − 12 pKb − 12 logC
Kb b×C Kb

h =√K √
Kw Kw Kw×Ka
WA & WB Kh = 7 + 12 pKa − 12 pKb
Ka×Kb a×Kb Kb

Note: For amphiprotic anion (like HCO−

3 ):

pK1+pK2
pH = 2

8. Buffer Solution:

(i) Buffer solutions are resistive in nature for pH change.

(ii) On dilution, pH of the buffer solution remains unchanged.

(iii) When small amount of strong acid or strong base is mixed in buffer solution, pH of buffer solution remains almost unchanged.

9. Types of Buffer Solution:

(i) Simper buffer solution (aqueous solution of weak acid + weak base salts).
(ii) Mixed buffer solution:

(a) Acidic buffer solution (weak acid + weak acid & strong base salts).

(b) Basic buffer solution (weak base + weak base & strong acid salts).

Henderson-Hasselbalch equation for buffer:

[conjugate base ]
Acidic: pH = pKa + log
[weak acid]

[ conjugate acid ]
Basic: pOH = pKb + log
[weak base]

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17. Solubility Equilibria of Sparingly Soluble Salts:

For a salt, AxBy ⇌ xAy+ + yBx−

(i) Ksp > Instantaneous ionic product ⇒ unsaturated. (More salt can be dissolved)

(ii) Ksp = Instantaneous ionic product ⇒ saturated. (No more salt can be dissolved)

(iii) Ksp < Instantaneous ionic product ⇒ super saturated ⇒ precipitation occurs.

10. Group Precipitation:

Group Radicals Condition for precipitation (Group reagent) Forms of precipitation

Zero Na+,K+,NH*4 1 − 2 drops of CH3COOH -

Pb+2,Hg+1 Chloride
First By mixing dilute HCl
(Hg+2
2 ),Ag
+ AgCl,Hg2Cl2,PbCl2

Sulfide PbS, HgS, CuS,CdS,

Pb+2,Cu+2,Hg+2, Cd+2,
Second H2S gas passed in the presence of acidic medium SnS, SnS2,As2 S3,
As+3, Sb+3,Sn+2, Sn+4.
Sb2S3, Bi2 S3.

Hydroxide Al(OH)3,Fe(OH)3,
Third Al+3,Cr+3,Fe+3 NH4OH mixed in the presence of NH4Cl
Cr(OH)3

Fourth Zn+2,Ni+2, Mn+2, Co+2 H2 S gas passed in the presence of basic medium Sulfide MnS,CoS, NiS, ZnS
Fifth Ba+2,Sr+2,Ca+2 (NH4)2CO3 mixed in the presence of NH4Cl Carbonate BaCO3, SrCO3, CaCO3
Sixth Mg+2 By mixing Na2HPO4 Hydrogen phosphate (MgHPO4)

(i) For precipitation of common salt (NaCl), HCl gas is passed & for soap (C 17H35COONa),NaCl is mixed.

(ii) Ionization of weak electrolyte is decreased in the presence of common ion is called common-ion effect.

(iii) Solubility product of the sparingly soluble salt A×By with solubility (s) mole/liter in saturated solution
x+y
AxBy ⇌ xAy+ + yBx− Ksp = xxyy (s)
(iv) Salt analysis of inorganic mixture depends on the common-ion effect and values of solubility products.

(v) In the presence of common ion, solubility of weak electrolyte always decreases. Solute A+B− is precipitated if [A+] [B−] > Ksp.

11. Indicator:

(i) For acidic indicator [HIn], For basic indicator (InOH):

Hln ⇌ H+ + In− InOH ⇌ In+ + OH−

[In −] [In +]
pH = pKIn + log [HIn] pOH = pKIn + log [lnOH]

(ii) Color change of the indicator is explained by:

(a) Ostwald's theory

(b) Quinonoid theory

Name of indicator Color in acidic medium Color in basic medium Working pH range of indicators
Methyl orange (MeOH) Orange red Yellow 3.1 to 4.5
Methyl red Red Yellow 4.2 to 6.2
Phenol red Yellow Red 6.2 to 8.2
Phenolphthalein (HPh) Colorless Pink 8.2 to 10.2

12. Acid-base Titration:

Type of titration pH range of titration Suitable indicators

Strong acid/strong base 3 − 11 All indicators ( MeOH, HPh etc.)
Strong acid/weak base 3 − 7 Methyl orange (MeOH) and methyl red
Weak acid/strong base 7 − 11 Phenolphthalein (HPh)
Weak acid/weak base 6.5 − 7.5 Phenol red

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Chapter - Aldehydes, Ketones and Carboxylic Acids

1. Methods of preparation of carbonyl compounds:

*only used for preparation of aldehyde .

2. Chemical properties of carbonyl compounds:

3. Some other important reactions:

(i) Perkin Condensation:
H3CCOONa
C 6H5CHO + (CH3CO)2O −−−−−−→ C 6H5CH = CH − COOH
(ii) Beckmann Rearrangement:

The acid catalyzed conversion of ketoximes to N-substituted amides is known as Beckmann rearrangement.

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 (iii) Cannizzaro’s reaction:
This reaction is preferentially given by those aldehydes which do not contain α-hydrogen. In Cannizzaro reaction, one molecule of the aldehyde is oxidized to acid at the expense
of the other which is reduced to alcohol i.e., disproportionation reaction takes place. The reaction occurs in the presence of concentrated solution of any base.

2HCHOFormaldehyde + NaOH → HCOONaSod. formate + CH3OHMethyl alcohol

4. Some important points of carbonyl compounds:
(i) Distinction between formaldehyde, acetaldehyde, and acetone:

S.No. Reagent/Test HCHO CH3CHO CH3COCH3

I. Brady reagent/DNP Colored crystal Colored crystal ×

II. Tollen's reagent Silver mirror Silver mirror ×

III. Fehling's solution Red Red ×

IV. Benedict’s solution Red Red ×

V. Corrosive sublimate (HgCl2) Black Black ×

VI. Schiff's reagent Pink Pink ×

VII. Iodoform test × yellow Yellow

VIII. Pyrogallol test White × ×

IX. Legal test (Sodium nitroprusside/NaOH) × Red Red

X. m − nitrobenzaldehyde test × × Blue

(ii) Chloral (CCl3CHO) is an important intermediate in the manufacture of chloroform and D.D.T.

(iii) Popoff's rule: Oxidation of unsymmetrical ketones largely take place in such a way that the smaller alkyl group remains attached to the CO group during the formation of two
molecules of acids.

(iv) Formaldehyde is used in preparation of urotropine (Hexamethylenetetramine), a urinary antiseptic and Bakelite (phenol-formaldehyde resin) polymer, throat lozenges (formalin
+ lactose).
(v) Formaldehyde is used as disinfectant and preservative for biological specimens in the form of formalin.
5. Methods of preparation of carboxylic acids:

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6. Chemical properties of carboxylic acids:

Heating effect on carboxylic acids

7. Carboxylic acid derivatives:

These are formed by the replacement of − OH group of acid by some other suitable group e.g. RCOCl, RCONH2, RCOOR and (RCO)2O.

(i) Acid halides:

Chemical Properties:

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(ii) Acid Anhydrides:

(RCO)2O, prepared by dehydration of carboxylic acid.

Chemical Properties:

(iii) Esters:

RCOOR prepared by reaction of acid with alcohol or acid chloride or anhydrides with alcohol.
Chemical Properties:

(iv) Acid amides:

RCONH2− It is prepared by reaction of carboxylic acid or its derivatives with NH3. It is amphoteric in nature. Acid amides act as weak acids as well as weak bases. Lone pair of
N is delocalized with π electrons of C = O group.
Chemical Properties:

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