SU.

M,MARY Chapter
._( -(-

I
H:

I
!hi

-(-(-

x
HX

I I I

x
I I X

I

-(-(i"-i

co ncentr ated
'H2.504 <,
(=(

-c-(I I
!WI

water

-C~(
I HI I OFli

/'

05031-1

ha Io'g:el! wa~e r,
X·OH

-(-cI I X Or!

i!:jtj dlfied

K Mn 04,

cold

-c-(I I
OHi OFR
.' ~.

acidified KMn04.

hot

<,

,,-/

- (·=0+ -

~:C =0 ,,~

'-----------11-

02, 50i lver

cata i'yst

- ( _.c

I

I

-

vJater
-~---j)!r -

C~

CI
OH

I

~/

o

I
OH

""

TESTS' FOR'FUN'crioNAl"GRC)UPS'
-, / -, I I

.

1 Alkenes (a) With a solution of bromine in tetrachloromethane (Room temperature): The reddish-brown colour of bromine is decolourized.
Testing of alkenes with bromine solution
--

.--

-_-

..""

/

C

=

c

+ Br2,

--+

-

C-

I

cI

Br Br (b) Heated slowly with an acidified solution of potassium manganate(VII). The purple colour of potassium manganate(VII) is decolourized.

Testing of alkenes with potassium manganate(VII)
......... - I""

-, /

c=c

/ -,

+ H20 + [0]

-cs-

-

c- cI I
OH OH

I

I

2 Halogenoalkanes Heat with aqueous ethanolic silver nitrate. (a) Chloroalkane: White precipitate (b) Bromoalkane: Cream precipitate (c) Iodoalkane: Yellow precipitate
R-X + H20 + Ag"

~

Testing of halogenoalkanes with ethanolic silver nitrate

~

:

--

R-OH + H+ + AgX(s)

3 Benzene Heated slowly with a mixture of concentrated nitric acid and concentrated sulphuric acid. Pour the products into cold water : A layer of yellow oil is observed. N0

©

+HNO,

-

©

2

+H20

Testing of benzenes with concentrated acids "... :

.(l
:

.....................................

4 The -OH group Add solid phosphorus(V) chloride (Room temperature): White fumes given off. R-OH + PCl5 -RCI + POCl3 + HCl(g)
RCOOH + PCl5
--

RCOCI + POCl3 + HCI(g)

......

Testing of -OH group with PCls
-

~ :
:

5 The carbonyl group (aldehyde and ketone) Add 2,4-dinitrophenylhydrazine (Room temperature): An orange precipitate is formed. N02 ~C = 0 + H2N -NH---@-N02
6 Aldehydes

N02 ~C = N -NH---@N02 + H20

..................................

Testing of carbonyl group with 2,4-dinitrophenylhydrazine:

Q. :

(a) Heat with Fehling's solution: A brown precipitate is formed.
RCHO + 2Cu2+ + 50H-

--

RCOO- + 3H20 + Cu20(s)

(b) Heat with Tollen's reagent: A silver mirror is formed. RCHO + 2[Ag(NH3

Testing of aldehydes ~ with Fehling and Tollen's reagents
...................................

:
=

)l + 20Er

~ RCOO- + 2Ag(s) + 3NH3 + 2H20 + NH/ : Effervescence.

7 Carboxylic acids Add aqueous sodium carbonate (Room temperature)
2RCOOH + Na2C03 8 The benzoate ion
--

2RCOONa + H20 + CO2

Testing of carboxylic acids with sodium carbonate
-!l,

~

:

(a) Dissolve the salt in water followed by dilute sulphuric acid: A white precipitate is formed. CsH5COO- + H+ -CSH5COOH(s) (b) Add aqueous irontl ll) chloride (Room temperature): A buff precipitate is formed. 3CsH5COO- + Fe3+ -(CsH5COO)3Fe(s) and HCI): 9 Primary amines Warmed with aqueous nitric(III) acid (a mixture of NaN02 Effervescence is observed.
RNH2 + HN02
-.>0

...............................

Testing for benzoate ions with (a) sulphuric acid (b) iron(lll) chloride

-(f
-

.... :

......

Tes~ing for primary arrunes with aqueous nitric acid

.(!j
: :

ROH + H20 + N2
Testing for amides with ~ aqueous sodium hydroxide
-of "

10 Amides Warmed with aqueous sodium hydroxide: Ammonia gas (which turns moist red litmus blue) liberated.
RCONH2 + NaOH

--

RCOpNa + NH3

: :
:

~ .

Testing for acyl chloride with (a) water (b) aqueous silver nitrate

:

~
Testing for phenols with (a) bromine water (b) aqueous ion

~ : . :

11 Acyl chloride (a) Add a little water (Room temperature): White fumes given off. RCOCI + H20 -. RCOOH + HCI(g) (b) Add aqueous silver nitrate: White precipitate formed immediately. RCOCI + H20 +Ag+ RCOOH + AgCl(s) + H+ 12 Phenols (a) Add bromine water (Room temperature): White precipitate formed.

....

-

srwsr
OH
~
Sr

+3H",

~ :

Testing for phenylamines with bromine water

(b) Add aqueous iron(lII) chloride (Room temperature): Purple solution formed. 3C6H50H + Fe3+ (C6H50)3Fe 13 Phenylamines Add bromine water (Room temperature): White precipitate formed.

......................................

14 The CHa-CH-R and CHa-C-R groups

~Testing for methyl : alcohols or methyl carbonyl compounds with alkaline iodine solution : ..

I

II

Heat with a solution of iodine in aqueous sodium hydroxide: Yellow precipitate formed. CHa-CH-R + 412 + 6NaOH - RCOONa + 5Nal + 5H20 + CHI3(s) I OH
CHrC-R

OH

0

~ : : ~ :

Testing for ethanoate ion with aqueous iron(lll) chloride

..

15 The ethanoate ion, CHaCOOAdd aqueous irorufll) chloride (Room temperature) solution formed.

o

II

+ 312 + 4NaOH -. RCOONa + 3Nal + 3H20 + CHI3(s)

: A reddish-brown

3CH3COO- + FeCl3 -... (CH3COO)3Fe(aq) + 3Cr 16 Ethanedioic acid, H2C204 or the ethanedioate ions, C20i-. Add acidified potassium manganate(VII) then warm the mixture: The purple colour of potassium manganate(VII) is decolourized on warming. 2Mn04- + 5C20l- + 16R+ - 2Mn2+ + 10C02 + 8H20 17 Methanoic acid HCOOH. Warm with aqueous mercuryrll) chloride. A white precipitate is formed. RCOOH + 2HgCl2 Hg2C12+ CO2 + 2HCI 18 AIkylbenzene Warmed with acidified potassium manganate(VII): Purple potassium manganate(VII) is decolourized.

Testing for ethanedioic acid and ethanedioate ions with acidified potassium manganate(VII)

: ~ : Testing for methanoic acid with aqueous mercury{lI) chloride

~

.................................
~ : : Testing for alkyl benzene with acidified potassium manganate(VII)

colour of

....

@-

CR3 + 3[0]

-

@-

COOH + H20

Activation energy The minimum amount of energy required for a chemical reaction to occur. Allotropy A phenomenon where an element can exist in more than one form. The different forms of an element are called allotropes. Examples: Carbon (diamond, graphite); sulphur (rhombic and monoclinic); oxygen (oxygen and ozone, 03)' Anode The electrode where oxidation occurs. Arrhenius acid A chemical substance that dissociates to form hydrogen ions H+ when dissolved in water. Arrhenius base A chemical substance that dissociates to form hydrogen ions H+ ions when dissolved in water. Autocatalysis A reaction where one of the products can act as a catalyst for the reaction. Avogadro's law At constant temperature and pressure, all gases of equal volumes have the same number of moles. Avogadro's number The number of atoms in exactly 12.0000 g of carbon-12 (6.023 x 1023). Azeotrope A mixture of liquids at a constant boiling point where the composition of the vapour is the same as the composition of the liquid. The composition of the azeotrope remains unchanged on distillation. Boiling point The temperature at which the vapour pressure of a liquid is equal to the atmospheric pressure. Bond energy The amount of heat energy required to break a covalent bond in a gaseous molecule per mole of the bond. Boyle's law The volume of a fixed mass of gas at constant temperature is inversely proportional to its pressure. Bronsted-Lowry Bronsted-Lowry acid A proton donor.
,

Chromatography The technique to separate and to identify the various components in a mixture. • ' • Common ion effect The shift in equilibrium caused by addition of a compound having an ion similar to one of the ions formed from the dissolved substances. Complex ion An ion containing a central metal cation or an atom that is bonded to a group of ligands by coordinate bonds. Co-ordinate covalent bond A covalent bond where both the shared electrons are contributed by one of the two bonded atoms. • Co-ordination number (complex ion) The number of donor atoms that surround the central metal cation or atom in a complex ion. It is also equal to the number of co-ordinate bonds formed by the central atom or ion with ligands. [Note: It is not the number of ligands that surrounds the central ion or metal. Some polydentate ligands can form more than one co-ordinate bond per ligand with central ion or atom]. Co-ordination number (solid) The number of atoms, molecules or ions surrounding a given particle in the solid lattice structure. Covalent bond The electrostatic attraction between two adjacent nuclei and the pair of electrons that are shared between them. Critical point The temperature above which a gas will not liquefy by increasing pressure only. Critical pressure The minimum pressure required to bring about liquefaction of a gas at the critical temperature. Dalton's law of partial pressure The total pressure of a mixture of gases that do not interact with one another is given by the sum of the partial pressures of all the gases present. Dative bond A covalent bond where both the shared electrons are contributed by one of the two bonded atoms. • Degenerate orbitals Orbitals having the same energy.

, , • ' , . • ' •

base A proton acceptor.

Buffer capacity The amount of acid or base that needs to be added to a buffer solution to change its pH by one unit. Buffer solution A solution where its pH does not change significantly when a small amount of acid or base is added to it. Catalyst A substance that alters the rate of a chemical reaction without itself being altered. Catenation The ability of the atoms of an element to form bonds with one another. Cathode. The electrode where reduction occurs.

Degree of dissociation The fraction or percentage of the initial amount that has dissociated. Disproportionation A reaction in which the same substance is oxidised and reduced simultaneously. • Distribution (partition) law A solute will distribute itself between two immiscible liquid solvents such that the ratio of the concentrations of the solute in each solvent is a constant at constant temperature. The partition law is not obeyed for concentrated solution or when the molecular species in the two solvents are not the same.

Charles' law The volume of a fixed mass of gas at constant pressure is directly proportional to its absolute temperature.

,

Dynamic equilibrium The condition in which the rate of the forward reaction is equal to the rate of the reverse reaction and the amount of substances remains constant. Effective collisions Collisions that results in the formation of products. Collisions in the correct orientation and with sufficient energy to overcome the activation energy Electrochemical cell A device that converts chemical energy into electrical energy. Electrolysis The decomposition of an electrolyte by electrical current. Electrolyte A substance that conducts electricity either in the molten state or when dissolved in water. Electron affinity The heat change when a gaseous atom receives an electron, per mole of the atom. Electronegativity The relative strength of an atom to attract electrons in a covalent bond to which it is bonded. Enantiomers Compounds having the same molecular formula but are mirror images and are not superimposable. Enthalpy change of combustion The heat energy released when 1 mol of a substance is burnt completely in excess of oxygen under standard conditions. Enthalpy change of formation The heat. change \ "hen 1 mol of a substance is formed from its elements under standard conditions. Enthalpy change of hydration The heat change when 1 mol of ions dissolve in water to form hydrated ions under standard conditions. Enthalpy change of reaction The heat change that accompanies a chemical reaction. energy

Faraday's second law of electrolysis The relative amount of substances produced by the same quantity of electricity is inversely proportional to the charge on the ions. Fractional distillation A process for separating liquid components in a liquid mixt.ure based on their different boiling points. Free radical A neutral atom or molecule containing an unpaired electron. Free radicals are formed by the hemolytic fission of a covalent bond. Half-life The time taken for the amount of a substance to decrease to half its initial value. Henry's law The solubility of a gas in a solvent directly proportional to its partial pressure. Hess's law The enthalpy independent of its pathway. change of a reaction
IS

IS

Hybridisation The combining of two or more nonequivalent atomic orbitals to form a set of equivalent hybrid orbitals. Hydrogen bond The electrostatic attraction between a hydrogen atom bonded to an atom of a very electronegative element (N, 0 or Fl and the lone pair electrons of another very electronegative atom (N, 0 or F). Ideal gas A gas that obeys the ideal equation perfectly under all conditions. Ideal solution A solution that obeys Raoult's law. Ionic bond The electrostatic attraction between oppositely charged ions that are formed when electrons are transferred from one atom to another. Ionisation energy The minimum energy required to remove one electron from an isolated atom (or ion) in its ground state, per mole of the atom or ion. Isotopes Atoms of the same element (i.e. with the same proton number) but with different nucleon number. Lattice energy The heat released when 1 mol of an ionic solid is formed from its free gaseous ions under standard conditions. Le Chatelier's Principle When a system in dynamic equilibrium is subjected to a change, the position of equilibrium will shift in the direction to nullify the effect of the change so that the equilibrium is reestablished. Lewis acid A subtance that accepts a lone pair of electrons from another substance. Lewis base A substance that donates a lone pair of electrons to another substance. Ligand An atom, a molecule or an ion that is bonded to the metal atom or metal cation in a complex ion by coordinate bond. Matter Anything that has a mass and occupies space. Melting point The temperature at which the solid state and liquid state are in equilibrium.

Enthalpy change of solution The heat change when 1. mol of a substance dissolves in water to form a solution of infinite dilution under standard conditions. Enthalpy change of vaporisation The heat energy required to vaporise 1 mol of a liquid at its boiling point under standard conditions. Enthalpy of atomisation The heat energy required to produce 1 mol of free gaseous atoms from an element under standard conditions. Enthalpy of neutralisation The heat energy given off vhen 1 mol of water is formed from the reaction between an acid and a base under standard conditions. Equilibrium constant The ratio of the equilibrium concentration of the products to the equilibrium concentration of the reactants each raised to the power of their respective stoichiometric coefficient. Faraday (F) The amount of charge contained in 1 mol of electrons. Faraday'S first law of electrolysis The amount of substance produced during electrolysis is directly proportional to the quantity of electricity that passes through the electrolyte.

Metallic bond The electrostatic attraction between metal cations and the 'sea' of delocalised electrons in a solid lattice. Metalloid non-metal. An element with properties of metal and

Rate-determining step The slowest step in a sequence of steps that leads to the formation of products. It is also the step with the highest activation energy. Reducing agent A substance that donates electrons to another substance. Reduction Relative A process of electron gain. atomic mass The mass of one atom of the

Mole The amount of substance that contains the same number of elementary particles (atoms, molecules, ions or electrons) as the number of atoms in exactly 12 g of carbon-12. Nucleon number Number of protons and neutrons in the nucleus of an atom. Orbital A region in space where the probability of finding a particular electron is high (about 95% chance). Order of reaction The order of reaction is the sum of the powers to which the concentration of the reactants are raised 111 an experimentally determined rate equation. Rate = k[A]'[B:P' Order of reaction with respect to A is x. Order of reaction with respect to B is y. Overall order of reaction = x + y. Ostwald dilution law The degree of dissociation of a weak electrolyte is inversely proportional to its concentration. At infinite dilution (where concentration approaches zero), all weak electrolytes are fully dissociated. Overpotential The additional electrolysis to occur. Oxidation voltage required for

element relative to /2 times the mass of atom of carbon-12. Relative isotopic mass The mass of one atom of the

isotope relative to 112 times the mass of atom of carbon-12. Relative molecular mass The mass of one molecule to

of the element or compound relative mass of atom of carbon-12.

:2 times

the

Screening effect The repulsion between electronic shells that are filled with electrons. It also refers to the effect of shielding of the outermost electrons by inner electrons from the pull of the nucleus. Sigma (a) bond A covalent bond formed by the end-toend overlapping of atomic orbitals. The electron density of the bond is concentrated in the region between the nuclei of the bonding atoms. Solubility product The product of the concentration of the ions, in a saturated solution of a sparingly soluble salt, each raised to the power of its stoichiometric coefficient. Standard electrode potential (EON) The potential difference between an electrode and its aqueous ions of concentration 1.0 mol dm=', relative to that of the standard hydrogen electrode at 298 K and 101 kPa. Structural isomers Compounds having the same molecular formula but different structural formula. Transition metals Elements that can form at least one stable ion that has an incompletely filled d subshell. Triple point The temperature and pressure at which the solid, liquid and vapour phase of a substance can exist in equilibrium. van der Waals forces The intermolecular forces that holds molecules of covalent compounds together in the solid or liquid state.

A process of electron loses.

Oxidising agent A substance that can accept electrons from another substance. Partial pressure The pressure exerted by a gas, in a mixture of gases, if that gas alone occupies the same volume as the mixture at the same temperature. Pauli exclusion principle No two electrons atom can have the same four quantum numbers. in an

Pi (n) bond A covalent bond formed by the sideways overlapping of atomic orbitals (usually the p orbitals). The electron density of the bond is concentrated above and below the plane containing the nuclei of the two bonded atoms. Proton number of an atom. The number of protons in the nucleus

Raoult's law The partial vapour pressure of a liquid, A, in a mixture of immiscible liquids, is given by the product of the vapour pressure of pure A and the mole fraction of A in the mixture, at the same temperature. PA = XApOA

SUMMARY
H2, Ni catalyst
-(-(-

I
H
Halogen, X2

I
H

I

I

-(-(-

X
HX

I

X

I

-(-(-

I

I

H concentrated
H2SO4

X water

-(-(-

I
H

I
OS03H

-(-(I I
H OH

halogen water, X-OH

-(-(-

I X
acidified KMn04, cold

I
OH

-(-(-

I

I

OH acidified KMn04, hot

OH

~(=O+

-:

/

~(=O

02, silver catalyst

-(-(-

I

I

water

1 -( -(-

I

"'/

o

I
OH

I
OH

SUMMARY
; E;:ctions of Benzene cone. HN03

+ cone. H2S04, 50°C

@-@--

N02

C12, A12C16 or Fe catalyst

CI

RCI + A12C16

@-

-- @-~

R

RCOCI + AI2CI6

t-

@-@--

C-R
Il

Cone. H2SO4

0 S03H

~

H2, Ni catalyst

-@-

0
CH2C1 COOH

;;=actions

of Methylbenzene CI2 + light

acidified

KMn04,

heat @-

acidified

Cr203, heat @-CHO

CI2 + AI2CI6

@RX + AI2CI6 concentrated H2SO4

CH3

©rCl
CH3

CH3 and

c9J
CI CH3

--

©r
©r
CH3

CH3

R
and

c9J
R
CH3

503H

and

c9J c9J

S03H

cone. HN03

+ cone. H2SO4

©rNO'
CH3

CH3 and

N02

SUMMARY
Reactions of Halogenoalkanes NaOH(aq), reflux
~-------+

2
water ~------------------~ methanal, HCHO RH

Reactions of Grignard Reagents

R-OH

1---------+

concentrated ammonia

R-NH2

RCH20H (primary alcohol)

1----------+

ethanolic KCN

R-CN

1----------------+

other aldehydes, R'CHO

R - CH - R'

ethanolic R'COO ~------__. ethanolic R'ONa

R'COOR RMgX-

I
OH (seconda ry aleo :). ketone,
/

RX

--4-----------+

R'-O-R

R'

ethanolic NaOH

'"
/

R' /

"c == 0

-.

I R - C - R'
I

R'

C=C

'"

OH (tertiary alcohol)

I--------------__}I>

Na in ether

R-Na

1-----------------+

magnesium in ether

L------------+RCOOH
RMgX

SUMMARY
Reactions of Carboxylic Acids
NaOH electropositive metal

I-------------------------~

RCOO-+H2 RCOONa + effervescence (C02) RCOOR' RCDel + wh ite fu mes HCI

Na2C03 or NaHC03 f---------------------~ RCOOH R'OH. concentrated ----------------~~
I----------------------~

H2S04

PCls

reduction

SUMMARY
~::sctions of Alcohol sodium R'COOH, concentrated PCls KBr + concentrated H2SO4
12

a+ H2SO4

2

R'COOR
RCI + white RBr RI fumes of HCI

ROH

Red phosphorus + Excessof concentrated concentrated H2S04, 140

H2S04, 180 "C

\

0c. Excessalcohol

C=C / \

/

R-O-R
RCHO or RCOOH (for primary alcohol)

Acidified

KMn04

R-C-R (for secondary alcohol) II

°

""'eactions of Phenol sodium @NaOH O-Na +H2

@-

O-Na+

H2O

RCOCI

R-C-O
0
II

-<Q)

@

OH

White bromine water

8'*8r
OH Br

precipitate

FeCI3(aq)

blue/violet (@-OhFe

colouration

zinc powder,

heat

@

SUMMARY
1 Reactions of Aldehydes
OH I HCN

R-C-CN
I H OH I

NaHS03

R-C-SO;Na+ I
H

II R-C-H

°

2,4-dinitrophenylhydrazine

R
H

-,
/

C = N-NH

Acidified

K2Cr207

RCOOH

Tollen's reagent Fehling's solution Reduction Zinc amalgam + HCI

RCOO- + silver mirror RCOO- + reddish-brown
precipitate of Cu20

2

Reactions of Ketones R'
HCN
--'"

R-C-CN
I OH

I

R'
NaHS03 ...... I R-C-SO;Na+ I OH

R-C-R'

2,4-d initrophenyl hyd razi ne
--'"

°
Acidified KMn04, heat

II

R" R'/

C = N-NH

-@-

N02

....
--'"

R'COOH + CO2 + H2O R-CH-R'
I OH

Reduction

Zinc amalgam + HCI

--'"

RCH2R'

SUMMARY ch£1pter
Reactions of Derivatives (a) Acid chloride of Carboxylic Acids

30
fumes HCI

RCOOH + white

o
R-C-CIII

1---------------

R'OH N H3

RCOOR' RCONH2 RCONHR'

1-------------=-----.
L-

Concentrated

R'NH2

(b)

Ester Acidic hydrolysis Alkaline RCOOR' hydrolysis NH3

RCOOH + R'OH RCOONa + R'OH RCONH2 + R'OH

Concentrated Reduction,

UAIH4 in ether

(c)

Amide

r---------------_
Alkaline hydrolysis,

Acidic hydrolysis,

heat heat

RCOOH + NH4+

P4010 (Dehydration) RCON H2 --+----__:___:_::__:__-.:;__-----=---~--------------Br2 + KOH Reduction

RCN RNH2

(d)

Odours of some esters
-

Ester
Methyl butanoate Penthylethanoate Ethyl butanoate Ethyl methanoate

Formula
CH3CH2CH2COOCH3 CH3COOCHzCH2CH2CH2CH3 CH3CH3CH2COOC2Hs HCOOCzHs

~

1

-

i ,

Smell
Apple Banana Pineapple Rum

SUMMARY
Reactions of Alkylamines
r-.:....:

H::_20

e-Oo

RNH/ RNH3+

+ ow

dilute
RNH2~~
L_ __

acid,

W
___
e-Oo

~HN~O~2 ~R_'C_O_C_I

ROH

+ effervescence

(N2)

R'CONHR

Reactions of Phenylamines
@-NH/

~_:_H.:..:.N.:....:O:....:2::...' -h-e-at-----------..._@-OH+efferveSCenCe(N2)

RCOCI

RCONH

--@

L_::b:_:_ro=-ffi:_:__:_:_:_i n.:....:e:_w_at_e_r

~.... Wh ite precipitate,

Reactions of Benzene Diazonium ion
H20
@-OH

KI{aq)

_..

@-I

CuCiJHCI
@-CI

CuCN/KCN

....

@-CN

(Q)- OH/NaOH
@-N=N

-@-

OH

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