Electronegativity is defined as follows Electronegativity is the ability of an atom within a covalent bond to attract the bonding 4air of electrons. The table below shows electronegativity values of main block elements H 2.1 Li Be 1.0 1. "a (g 0.' 1.2 !a 0.+ 1.0 0b *r 0.+ 1.0 !s Ba 0.+ 0.' B 2.0 )l 1. .a 1./ 1n 1.2 Tl 1.+ ! 2. *i 1.+ .e 1.+ *n 1.+ ,b 1.+ " #.0 , 2.1 )s 2.0 *b 1.' Bi 1.' $ #. * 2. *e 2.& Te 2.1 ,o 2.0 % &.0 !l #.0 Br 2.+ 1 2. )t 2.2 He "e )r -r 3e 0n
This occurs if each of the atoms have the same 4ull on the electron 4air in the bond 6e5ual electronegativity7. 1t can be found in molecules of elements such as $ 28 Br2 and "2. *ince the atoms in each of these molecules are the same they will have the same electronegativity.
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1n most com4ounds however one atom will have a greater electronegativity than the other8 and so will have a greater 4ull on the electrons8 so distorting the electron region.
This 4rocess of moving away from the 4erfect e9am4le is called #olarisation. The e9tent of the 4olarisation will de4end on the difference in electronegativity of the two atoms. The 4olarisation of a covalent bond will mean that one 4art of the molecule is more negative 6the most electronegative atom7 than the other and causing the bond to be 4olar. Hydrogen chloride is an e9am4le of a molecule which contains a #olar !on". The chlorine 4ossesses a higher electronegativity8 so will draw the electron 4air in the covalent bond towards itself.
Cl
3.0
2.1
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Inter$e"iate !on"ing
1n :nit 1 61onic Bonding7 it was noted that ionic com4ounds can be 4olari;ed which gives them a covalent character. <hen a molecule has a 4olar bond8 it gives the covalent substance an ionic character. To regard a com4ound as =covalent> or =ionic> is too sim4listic for understanding )* chemistry. 1t is more correct to visuali;e ty4e of bonding on a sliding scale where com4ounds can be described as =#re"o$inantly covalent > or =#re"o$inantly ionic>. Electronegativity values can be used to give an a44ro9imate idea of the 4redominant ty4e of bonding in a binary com4ound. Electronegativity difference ,ercentage ionic character Electronegativity difference ,ercentage ionic character Electronegativity difference ,ercentage ionic character Electronegativity difference ,ercentage ionic character 0.1 0. 0.' 1' 1.2 1 2. 2' 0.2 1 1.0 22 1.+ 2./ +2 0.# 2 1.1 2/ 1.' ' 2.2 +& 0.& & 1.2 #0 2.0 /# 2.+ +/ 0. / 1.# #& 2.1 /2 2.' ++ 0./ ' 1.& #' 2.2 20 #.0 +' 0.2 12 1. &# 2.# 2& #.1 '1 0.+ 1 1./ &2 2.& 2/ #.2 '2
Looking at a selection of substances *ubstance !hlorine8 !l2 )mmonia8 "H# <ater8 H2$ !alcium chloride8 !a!l2 Lithium o9ide8 Li2$ ,otassium fluoride8 -% Elect?y value 1 #.0 #.0 #. #.0 #. &.0 Elect?y value 2 #.0 2.1 2.1 1.0 1.0 0.+ Elect?y difference 0 0.' 1.& 2.0 2. #.2 @ ionic ch?r 0 1' #' /# 2' '2
1f these are then 4lotted on the diagram below8 it can be seen the ty4e of bonding is a continuum rather than a black and white 4icture. 10 20 #0 &0 @ ionic character 0 /0 20 +0 '0 100
H2$
Cl2
NH3
H2O
CaCl
2
Li2O
KF
-3-
Cl
3.0
2.5
To decide whether a molecule will be 4olar8 it is necessary to look at where the centres of 4ositive and negative charge are 4laced. ) molecule of trichloromethane is 4olar
H + Cl Cl C
Centre of negative charge
Cl
Cl C Cl Cl Cl
Centre of oth negative an! "o#itive charge
*ince there is no se4aration of charge in tetrachloromethane this is not a 4olar molecule. )nother e9am4le of a molecule with 4olar bonds8 but is nonB4olar overall is carbon dio9ide.
3.5
+ 2.5
3.5
-4-
$ne way of testing a substance to see if it is com4osed of 4olar molecules is to 4lace an electrostatic charge near a Cet of the li5uid.
$%rette no&&le Charge! ro! 'he charge on the "olar (olec%le ca%#e# the (olec%le# to e attracte! to the charge! ro!.
The greater the angle of deflection the more 4olar the molecule.
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+,-
INTERMOLECULAR FORCES
%orces of attraction must e9ist between atoms and molecules which are not chemically bonded because at a low enough tem4erature all substances become li5uids or solids A even helium8 which consists of inert8 uncombined atoms. The three ty4es of 1ntermolecular force to be considered areD Di#ole & "i#ole attractions Lon"on or van "er 'aals( orces) and *y"rogen !on"ing.
H + C
Cl Cl
Cl
1n a 4olar material there is an attraction between the 4ositive charge in one molecule and the negative charge in the other.
+ - + + +- + + + +
-)-
)s the molecular mass of the gases increases8 the atoms contain more electrons and so the si;e of the van der <aal?s forces increases. )s the attractive forces between the molecules increases8 it becomes more difficult to se4arate the molecules from each other and so the boiling 4oints increase.
-*-
*y"rogen Bon"ing
Hydrogen bonds8 with energies usually in the range from 20B&0 kI mol A18 are ty4ically ten times as strong as van der <aals? forces8 and about oneBtenth as strong as covalent bonds. Two conditions are necessary for formation of hydrogen bondsD 6i7 ) H atom must be covalently bonded to a highly electronegative atom usually "8 $ or %. Hydrogen only has one electron which is used when hydrogen bonds to another element. The elements listed above are highly electronegative and so draw the electron 4air in the bond towards themselves. This leaves the 4roton on the hydrogen e94osed. + -
H
-roton e."o#e!
6ii7 The adCacent molecule must have a lone 4air of electrons on an "8 $ or % atom. The hydrogen8 with its K charge8 is strongly attracted to the adCacent lone 4air. This is more than Cust a 4olar attraction8 and is strongly directional 6along the line of the lone 4air7. Lou need to draw it with the 4olar bonds and lone 4airs marked. + + -
H
Lone "air
,
H/!rogen on!
H
-roton e."o#e!
(olecules which show hydrogen bonding between molecules includeD i7 H%E ii7 all com4ounds with A$H grou4s8 including waterE iii7 all com4ounds with A"HA grou4s8 including "H #. 1n addition these molecules can all hydrogenBbond to water.
-+-
H N
H N
H
+
'ater
H
-
O
*y"rogen l%ori"e
H O
-
F F
+ +
-0-
The three molecules below illustrate the various strengths of these intermolecular forces.
H 3C
CH2
CH3
,ro4ane is com4osed of nonB4olar molecules and so only has van "er 'aals orces between the molecules.
(etho9ymethane has a similar molecular mass to 4ro4ane8 but has a higher boiling 4oint because the molecules are 4olar8 so there are "i#ole&"i#ole attractions as well as van der <aals forces.
- + H3C OH CH2
4thanol1 .". 2 *+oC
Ethanol has .y"rogen !on"ing which is significantly stronger than the other intermolecular forces and so a much higher boiling 4oint than metho9ymethane even though they have the same molecular mass.
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00
&00
#00
200
100
The boiling 4oints of the alkanes increases with molecular mass. This ha44ens because the higher the molecular mass8 the greater the number of electrons and so the greater the chance of an imbalance and formation of an instantaneous di4ole. The van der <aals? forces 6London forces7 increase.
0 1 2 # & / 2 + ' 10 11 12
The melting 4oint of the alkanes increases with molecular mass for the same reason8 but the 4attern is not so straightforward as the different 4acking of molecules in the solid according to whether the number of carbon atoms is odd or even causes an additional factor in the determination of the melting 4oints. The closer the molecules are able to a44roach each other8 the greater the induction effect and so the greater the van der <aals? forces. <hen an alkane has branching 4resent8 the molecules cannot a44roach each other so closely and there is less area over which contact can occur8 so branched alkanes have lower boiling 4oints. The table below illustrates the effect of branching in alkane molecules on the boiling 4oint. )lkane Butane (ethyl4ro4ane (olecular mass / / *tructural formula !H#!H2!H2!H# !H#!H6!H#7!H# *keletal formula Boiling 4oint B0. o! B11.2 o!
-12-
20
B&0
B/0
B+0
-13-
H2 O
300
$oiling -oint5K
HF NH 3
200
100
-erio!
-14-
Sol%!ility
1n general a solvent will dissolve a substance that contains similar intermolecular forces.
+ +
+ + -
+ +
+ + -
+ +
+ + -
+ - + + -
*ome ionic com4ounds do not dissolve in water because the electrostatic attraction between the ions8 the Lattice ent.al#y8 is too great for the water molecules to overcome. To be soluble the energy 4roduced by hydrating the ions 6 t.e .y"ration ent.al#y7 must be more negative than the energy holding the ion together 6 t.e lattice ent.al#y7.
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-1)-