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Lecture 4: Intermolecular Forces

(Chemistry in Context Ch. 9 & ChemFactsheet 5)


Dipole-dipole attractions -polarisation and polar bonds -polar bonds and polar molecules shape and symmetry -effect on melting point and boiling point -ion-dipole forces and salt dissolution

Van der Waals (vdW) forces -evidence for van der Waals forces -temporary and induced dipoles -boiling points of alkanes
The hydrogen bond -formation of hydrogen bonds -effect of hydrogen bonding on b.p. of hydrides -important hydrogen bonded structures: ice, carboxylic acids, DNA Summary -three types of intermolecular forces -relative strength and influence on physical properties

Polar Covalent Bonds and O O Electronegativity (9.2) H H


In the C-C bond of ethane, for example electron density is exactly symmetrically
H C C H H H

homonuclear diatomic molecule

Most bonds are between extremes: H d+ dC N polar covalent bonds electron density is not transferred between H atoms but is unequally shared H C CF3

polar covalent bond

H
ionic bond other extreme very different atoms so electrons completely transferred K+

Cl-

ionic bond

e.g. in H-F most electron density is on fluorine leaving H partially positive molecule is polar
F is more electronegative than H electronegativity the tendency of an atom to attract electron density towards itself in a chemical bond

The greater the difference in electronegativity between two elements, the greater the polarity of the bond

-if electronegativity difference >1.8 compound is mostly ionic:

Cs+
+

P2O5 (difference = 1.4) completely covalent Li LiI (difference = 1.5) partly ionic, partly covalent Al2O3 (difference = 2.0) mostly ionic, slightly covalent CsF (difference = 3.3) completely ionic

F -

Electrostatic Potential Maps

electron-poor carbon

d-

-computer modelling alows electron rich (d-) and electron poor (d+) regions of molecule to be represented using colours of the rainbow

d+
d+

delectron-rich carbon

Bond Polarity (9.1) Q: One bond is indicated (by ) in each of the following: Indicate the polarity of each bond in each case:

H3CI H3CB(CH3)2

OCH2

BrMgCH3

(use d+ and d- to show electron density) Which molecules have zero dipole moment?

Bond Polarity (9.1) Q: One bond is indicated (by ) in each of the following: Indicate the polarity of each bond in each case:

d+ dH3CI dd+ H3CB(CH3)2

d- d+ OCH2 dd+ BrMgCH3

(use d+ and d- to show electron density) Which molecules have zero dipole moment?

Molecule Polarity (9.1) -bond polarity can cause the entire molecule to become possess a dipole moment (m) e.g.

H C

dichloromethane (m = 1.6 D)

difluoromethane (m = 2.3 D)

H C

Cl Cl

F F

Molecule Polarity (9.1) -bond polarity can cause the entire molecule to become possess a dipole moment (m) e.g.

H C

dichloromethane (m = 1.6 D)

difluoromethane (m = 2.3 D)

H C

Cl Cl

F F

-but sometimes dipoles within molecule cancel each other due to symmetry e.g.
m=0D

Cl C Cl
m=0D

F Cl F B F

Cl

Be

Cl Cl

Dipole-dipole attractions (9.3A) (weak: 5-10 kJ/mol)

-polar molecules have higher boiling points than non-polar compounds

-electrostatic attraction between opposite charges on neighbouring molecules (molecules arrange themselves so mutual attraction occurs lower energy)

Molecule Polarity and Boiling Point

b.p. 180 C

b.p. 174 C

o-dichlorobenzene is said to be polar BUT p-dichlorobenzene is non-polar as electron density is symmetrical (greater thermal energy needed to separate molecules bound by dipole-dipole forces)

Molecule Polarity and Boiling Point

b.p. 180 C

b.p. 174 C

o-dichlorobenzene is said to be polar BUT p-dichlorobenzene is non-polar as electron density is symmetrical dipole-dipole attraction explains higher boiling point of o-dichlorobenzene

first isomer has greater dipole-dipole attractions - more heat needed to separate molecules into vapour higher boiling point:

db.p. 61 C

d+
b.p. 47 C

polar

non-polar

d+

d-

H3C F
-for small molecules presence of a polar bond can change the boiling point by a hundred degrees!

F b.p. -78 C F b.p. -188 C

van der Waals forces (9.3B) -BUT even non-polar molecules have some force between them -evidence: b.p. of noble gases and tetra-substituted methanes

CH4
-b.p. -162C

CF4
-129C

CCl4
77C

CBr4
190C

what causes non-polar molecules to be attracted to each other?

Explaining the van der Waals interaction (9.4) (2 kJ/mol)


-electron clouds become imbalanced and can induce partial charges (temporary electric dipoles) in neighbouring molecules

even non-polar
molecules attract each other slightly

bigger molecules > more electrons > more polarisable > bigger dipoles > higher boiling points: CH4 CF4 CCl4 CBr4

b.p.

-162C

-129C

77C

190C

- all atoms and molecules interact with London forces to some extent
-extent of van der Waals force depends on: -no. of electrons -surface area

-strength of van der Waals increases with molecular weight:


bigger molecules more electrons more polarisable bigger temporary dipoles stronger force higher boiling point CH4 b.p. -164C C3H8 -42C C5H12 36C C7H16 98C C9H18 151C

-boiling points of alkanes depend mainly on intermolecular van der Waals forces

van der Waals forces and molecule surface area


H H H H H C C C H C C H H H H H H
H H C H H H C H C C H C H H H H H

n-pentane (C5H12)
H

H C H H H H C C C H H H H C H H

2-methyl-butane (C5H12)

neopentane (C5H12)

-isomers have the same empirical formula (C5H12), same mass -extent of van der Waals forces depends on surface area

van der Waals forces and molecule surface area


H H H H H C C C H C C H H H H H H
H H C H H H C H C C H C H H H H H

n-pentane (C5H12) 36C


H

H C H H H H C C C H H H H C H H

2-methyl-butane (C5H12) 28C

neopentane (C5H12) 10C

-isomers have the same empirical formula (C5H12), same mass -extent of van der Waals forces depends on surface area

e.g. n-pentane has greatest area greatest v der W forces highest boiling point

Hydrogen bonding (9.5)


-uniquely strong type of dipole-dipole attraction involving H covalently attached to X (N, O or F)

-H atoms have strong partial positive charge (d+) when attached directly to 2nd period electronegative atom

Hydrogen bonding (9.5)

OH::::N (29 kJ/mol) OH:::::O (21 kJ/mol) NH:::::::N (13 kJ/mol)

-gives water its high b.p. (compare CH4; boils at 160 C)

hydrogen bonding in water

(very important forces in protein secondary structure and interaction of biomolecules)

Structure of Ice (9.8A)

hydrogen bonding in ice

-water molecules held in hydrogen bonded hexagonal lattice -open cage structure low density ice floats

Hydrogen bondings effect on boiling points (9.5)

compare boiling points of p-block element hydrides:

Hydrogen bondings effect on boiling points (9.5)

(predicted bps assuming no hydrogen bonding)

H2O HF NH3 CH4

-hydrogen bonding much stronger than other dipole-dipole interactions - drastically raises boiling points: (actual b.p. with hydrogen bonding)

no hydrogen bonding

(fig 9.10)

Hydrogen bonding in organic compounds (9.8B)

carboxylic acid

Hydrogen bonding in organic compounds (9.8B)

carboxylic acids form dimers via hydrogen bonding

Hydrogen bonding in organic compounds (9.8B)

carboxylic acids form dimers via hydrogen bonding


Q: Both of the following propylamine isomers have identical molecular weights. However their boiling points are quite different. How and why?

H2N

C H2

H2 C

CH3 CH3 H3C N CH3

Hydrogen bonding in organic compounds (9.8B)

carboxylic acids form dimers via hydrogen bonding


Q: Both of the following propylamine isomers have identical molecular weights. However their boiling points are quite different. How and why?

H2N

C H2

H2 C

CH3 CH3 H3C N CH3

hydrogen bonded b.p. = 48 C

no hydrogen bonds b.p. = 3 C

Hydrogen Bonding in Proteins (9.8D)


-non-covalent interactions between distant parts of protein chain: causes protein chains to fold in very specific shape (secondary structure)

key to proteins action


a-helix is a common rod-shaped secondary structural unit in proteins

a-helix

Hydrogen Bonding in Proteins (9.8D) -when protein chains align a b-sheet structure results:

b-sheet
-two dimensional creased sheet like arrangement

Base pair formation in DNA (9.8D)


-hydrogen bonds hold together bases in DNA double helix:

Base pair formation in DNA


two-stranded DNA double helix

-two strands of DNA hydrogen bond to and coil around each other forming a double helix:

(base pairs)

(base pairs)

Comparing strengths of different intermolecular forces


van der Waals dipole-dipole forces forces only hydrogen bonding

liquid

gas

-permanent dipoles are stronger than induced dipoles (v der Ws) -hydrogen bonds are stronger than dipole-dipole interactions

Intermolecular interactions in solutions ion-dipole (15-40 kJ/mol): when an ion is in a polar solvent, solvent molecules surround the ion burying their oppositely charged parts against the ion solvation of the ion

hydrated cation
compare: ion-ion interaction (200-400 kJ/mol): strong attraction between oppositely fully charged ions

Functional Groups and Physical Properties


molecules functional groups

determine
strength of intermolecular forces present

determines

compounds

physical properties
e.g.
solubility boiling point

INTERMOLECULAR FORCES SUMMARY


(non-covalent interactions)
van der Waals force (1-5 kJ/mol)
H3C CH3 CH3 H3C

dipole-dipole interaction (5-10 kJ/mol)

d+
H3C

dCl

Cl CH3

d-

d+

hydrogen bonding interaction (10-30 kJ/mol) H3C

dO d+ H CH3 H d+ O d-