2010 DHS Year 5 H2 Chemistry

TUTORIAL 8 : CHEMICAL BONDING

1 Describe the formation of each of the following chemical bonds with appropriate reference to calcium, sodium oxide and hydrogen chloride: ionic bond covalent bond metallic bond

(a) (b) (c)

Draw dotandcross diagrams to illustrate the bonds in (a) and (b), showing only the outer (valence) electrons for each atom.

1(a) Ionic bonds are formed in Na2O. To achieve stable noble gas configuration, atoms of Na lose one valence electron each to form positively charged Na+ cations atoms of O gain two donated electrons each to form negatively charged O2 anions electrostatic forces of attraction exist between the oppositely charged Na+ and O2 ions in a giant ionic lattice structure

+ 2 Na O

(b) Covalent bonds are formed in HCl. To achieve stable noble gas configuration, atoms of H and Cl share one valence electron each to form HCl molecules electrostatic forces of attraction exist between the nuclei and the shared pair of electrons between H and Cl atoms in a simple molecular structure

H Cl
(c) Metallic bonds are formed in Ca when: atoms of Ca lose valence electrons to form positively charged Ca2+ cations valence electrons are loosely held and delocalised, i.e. free to move within lattice electrostatic forces of attraction exist between the Ca2+ cations and sea of delocalised electrons in a giant metallic lattice structure

*2

W, X, Y and Z represent elements of atomic numbers 9, 13, 19 and 34 respectively. State the formula and the type of bonding for the compound which you expect to occur between W and X W and Y W and Z Y and Z X and Z

(a) (b) (c) (d) (e)

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W: Grp VII (nonmetal) 13 X: Grp III (metal) 19 Y: Grp I (metal) 34 Z: Grp VI (nonmetal) (a) Compound: XW3 (ionic bonds present) (b) Compound: YW (ionic bonds present) (c) Compound: ZW2 (covalent bonds present) (d) Compound: Y2Z (ionic bonds present) (e) Compound: X2Z3 (ionic bonds present)
3 Use the following table format for each of the following cases to draw the dotandcross diagram, describe the shape (by drawing the Lewis structure and stating the shape) and state the polarity of each molecule (where appropriate): Molecule/ion Dotand cross diagram Diagram of shape (Lewis structure) Shape Polarity (polar/non polar)

(a) CO

(a)* (b) (c) (d)* (e) (f)*

CH3+ SCl2 AsCl3 ClO3 POCl2+ ClF4

(h)* (i) (j)* (k)* (l) * (m)*

CH3 SbF6 N2O4 NO2 C2H6 C2H2

Species

DotandCross Diagram

Lewis Structure

Shape

Polar?

+
(a)* CH3
+

C H H

H H C H

+
Trigonal planar

(b) SCl2

S Cl Cl

S Cl

Cl

Bent

Polar

Species

DotandCross Diagram

Lewis Structure

Shape

Polar?

(c) AsCl3

Cl As Cl Cl

As Cl Cl

Cl

Trigonal Pyramidal

Polar

(d)* ClO3

Cl O

Cl O O O

Trigonal Pyramidal

Species

DotandCross Diagram

Lewis Structure

Shape

Polar?

+
(e) POCl2+

P Cl Cl

Cl O P Cl

Trigonal planar

F
(f)* ClF4

Cl F

F
Cl

F F

Square planar

F
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Species

DotandCross Diagram

Lewis Structure

Shape

Polar?

(h)* CH3

C H H

C H
F

Trigonal pyramidal

F F
(i) SbF6

Sb F
F F

F Sb F F

F
Octahedral

Species

DotandCross Diagram

Lewis Structure

Shape

Polar?

(j)* N2O4

O N O N

O O

O N N O

O O

Trigonal planar about each N

non polar

(k)* NO2

O N

N O O

Bent

Polar

Species

DotandCross Diagram

Lewis Structure

Shape

Polar?

H
(l)* C2H6

H C H H C H
H

H C C H

H H H

C H

Tetrahedral about each C

non polar

(m)* C2H2

C C

Linear about each C

non polar

4 (a)

NO3

Draw the dotandcross diagram and Lewis structure for each of the following species and indicate their shapes with reasoning. NO3 and NCl3

O O N O

O N

O O

There are 3 bond pairs and no lone pair around N To minimise repulsion, the 3 electron pairs are directed to the corners of an equilateral triangle NO3 is trigonal planar NCl3

Cl N Cl Cl

Cl

Cl Cl

There are 3 bond pairs and 1 lone pair around N To minimise repulsion, the 4 electron pairs are directed to the corners of a tetrahedron bond pairlone pair repulsion > bond pairbond pair repulsion NCl3 is trigonal pyramidal
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(b)*

POCl3 and IOCl3

POCl3

Cl O P Cl Cl

Cl P O Cl Cl

There are 4 bond pairs and no lone pair around P To minimise repulsion, the 4 electron pairs are directed to the corners of a tetrahedron POCl3 is tetrahedral IOCl3

Cl O I Cl Cl

Cl Cl I O Cl

There are 4 bond pairs and 1 lone pair around I To minimise repulsion, the 5 electron pairs are directed to the corners of a trigonal bipyramid bond pairlone pair repulsion > bond pairbond pair repulsion IOCl3 is distorted tetrahedral
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Draw the dotandcross diagram and Lewis structure for each of the following molecules and indicate whether they are polar or not. H2S and NCl3

(a)*

H 2S

H S H

S H

There are 2 bond pairs and 2 lone pairs around S, so H2S is bent Dipole moments associated with the polar bonds (SH+) do not exactly cancel out, giving rise to a nonzero overall dipole moment H2S is polar NCl3

Cl N Cl Cl

Cl

Cl Cl

There are 3 bond pairs and 1 lone pair around N, so NCl3 is trigonal pyramidal Dipole moments associated with the polar bonds (NH+) do not exactly cancel out, giving rise to a nonzero overall dipole moment NCl3 is polar
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(b)

CH3Cl and N2H4

CH3Cl

H C Cl H

There are 4 bond pairs and no lone pair around C, so CH3Cl is tetrahedral Dipole moments associated with the polar bonds (ClC+) do not exactly cancel out, giving rise to a nonzero overall dipole moment CH3Cl is polar N2H4

N H

N H H

N H H

H N H

There are 3 bond pairs and 1 lone pair around each N, so N2H4 is trigonal pyramidal about each N Dipole moments associated with the polar bonds (NH+) do not exactly cancel out, giving rise to a nonzero overall dipole moment N2H4 is polar

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6 (a)*

Explain the following observation as fully as you can with the aid of dotandcross diagrams and Lewis structures (where appropriate): SF4 exist but not OF4

SF4

OF4

F F S F F F O F

F F

For SF4 and OF4 to exist, There would be 4 bond pairs and 1 lone pair around S or O 10 electrons surrounding central atom S or O S, being an element in period 3, has availability of vacant lowlying d orbitals to accommodate electrons and therefore can expand beyond octet structure SF4 exists O, being an element in period 2, has absence of vacant low lying d orbitals to accommodate electrons and therefore cannot expand beyond octet structure OF4 does not exist

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(b)*

NO2

NO2+ is linear but not NO2 +

+ O N O O N O

There are 2 bond pairs and no lone pair around N To minimise repulsion, the 2 electron pairs are directed opposite to each other NO2+ is linear NO2

O N O

O N O

There are 2 bond pairs and 1 lone pair around N

To minimise repulsion, the 3 electron pairs are directed to the corners of an equilateral triangle bond pairlone pair repulsion > bond pairbond pair repulsion NO2 is bent

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(c)

PCl3 has a smaller bond angle than CCl4

PCl3

Cl P Cl

Cl

Cl

Cl Cl

There are 3 bond pairs and 1 lone pair around P To minimise repulsion, the 4 electron pairs are directed to the corners of a tetrahedron bond pairlone pair repulsion > bond pairbond pair repulsion PCl3 is trigonal pyramidal with bond angle of 107 CCl4

Cl
Cl Cl C Cl Cl

C Cl Cl Cl

There are 4 bond pairs and 0 lone pair around C To minimise repulsion, the 4 electron pairs are directed to the corners of a tetrahedron CCl4 is tetrahedral with bond angle of 109.5

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(d)

SO2 is polar but not XeF4

SO2

O S

S O

There are 2 bond pairs and 1 lone pair around S, so SO2 is bent Dipole moments associated with the polar bonds (OS+) do not cancel out, 6to a nonzero overall dipole moment SO2 is polar XeF4

F Xe F

F F

F Xe F

F F

There are 4 bond pairs and 2 lone pairs around Xe, so XeF4 is square planar Dipole moments associated with the opposite polar bonds (FXe+) exactly cancel out, giving rise to a zero overall dipole moment XeF4 is nonpolar

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*7

Draw the Lewis structure for each of the following ions based on the given shape. By considering the number of bond pairs and lone pairs of electrons around the central atom, deduce the total number of electrons around the central atom, charge of ion and oxidation number of the central atom: WF2a+ (bent shape) where W is an element in Group V

(a)

F W F
Charge of ion = 5 4 = +1

a+

Why not
a+ W F F

??

Electron pairs around W: 2 bond pairs and 1 lone pair

Oxidation number of W = 1 2(1) = +3

(b) XH2b (linear shape) where X is an element in Group VII

b H X H

Why not
H X H b-

??

Electron pairs around X in ion: 2 bond pairs and 3 lone pairs Charge of ion = 7 8 = 1 Oxidation number of X = 1 2(1) = 3

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(c)

ZCl3d (Tshape) where Z is an element in Group VI

Cl Cl Z Cl

Electron pairs around Z in ion: 3 bond pairs and 2 lone pairs Charge of ion = 6 7 = 1 Oxidation number of Z = 1 3(1) = +2
8 State the conditions necessary for high degree of covalent character in ionic bonds and high degree of ionic character in covalent bonds. Using your knowledge of ionic radius and electronegativity, suggest with reasoning, each of the following cases: (a) *the compounds with the smallest and highest degree of covalent character in their ionic bonds NaCl, Na2S, AlBr3 and Al2O3

High degree of covalent character in an ionic bond arises from a high degree of polarisation when cation has high positive charge and small ionic radius anion has high negative charge and large ionic radius High degree of ionic character in a covalent bond arises from a high degree of electron displacement when covalently bonded atoms have a large electronegativity difference between them For NaCl, Na2S, AlBr3 and Al2O3 : o charge: Na+ < Al3+ Cl < S2
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Br < O2

 ionic radius:

Na+ > Al3+

Cl S2

Br > O2

compound with lowest degree of covalent character in ionic bond: NaCl compound with highest degree of covalent character in ionic bond: AlBr3
Extra Practice: FeBr3, Fe2S3, BaCl2 and BaO

charge:

Fe3+ > Ba2+

Br < S2

Cl < O2 Cl > O2

ionic radius:

Fe3+ < Ba2+

Br > S2

compound with lowest degree of covalent character in ionic bond: BaO compound with highest degree of covalent character in ionic bond: FeBr3
Smallest diff in electronegativity Largest diff in electronegativity

(b) the compounds with the smallest and highest degree of ionic character in their covalent bonds HCl, Cl2 and ICl

electronegativity:

Cl > I > H Cl & Cl < I & Cl < H & Cl

electronegativity difference:

compound with lowest degree of ionic character in covalent bond: Cl2 compound with highest degree of ionic character in covalent bond: HCl

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Extra Practice: CO2, CCl4 and CH4

electronegativity:

O > Cl > C > H C & H < C & Cl < C & O

electronegativity difference:

compound with lowest degree of ionic character in covalent bond: CH4 compound with highest degree of ionic character in covalent bond: CO2
9 There are three main types of chemical bond (i.e. ionic, covalent and metallic) and six main types of chemical structure (i.e. giant metallic, giant ionic, giant molecular, giant molecular layered, simple molecular with intermolecular van der Waals forces of attraction, simple molecular with intermolecular hydrogen bonds).

Use the following table format to name the type of chemical bond and structure in each of the following substances (do not consider aqueous state) and state the nature of electrostatic forces of attraction (eg. between oppositely charged ions) that must be overcome during melting/boiling. Substance (a) Mg (a)* (b) (c) (d)* (e)* (f)* (g)* Mg S8 Si H2O SiO2 SiCl4 Ar (h)* (i)* (j) (k) (l) (m)* (n)* C(graphite) HCl P4 CH3OH CH3F FeSO4 (CH3)3N Chemical bond Chemical structure Electrostatic forces of attraction overcome during melting/boiling

Substance (a) *

Chemical bond

Chemical structure

Electrostatic forces of attraction overcome during melting/boiling

Mg S8

metallic covalent

giant metallic simple molecular

between cations and sea of delocalised electrons intermolecular van der Waals forces of attraction (temporary dipoledipole interactions) between nuclei of atoms and shared pair of electrons (covalent bonds)

(b)

(c)

Si

covalent

giant molecular

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Substance (d) * (e) *

Chemical bond

Chemical structure

Electrostatic forces of attraction overcome during melting/boiling

H 2O SiO2

covalent covalent

simple molecular giant molecular

intermolecular hydrogen bonds between nuclei of atoms and shared pair of electrons (covalent bonds) intermolecular van der Waals forces of attraction (temporary dipoledipole interactions) van der Waals forces of attraction between atoms (temporary dipoledipole interactions) between nuclei of atoms and shared pair of electrons (covalent bonds) intermolecular van der Waals forces of attraction (permanent dipoledipole interactions) intermolecular van der Waals forces of attraction (temporary dipoledipole interactions) intermolecular hydrogen bonds intermolecular van der Waals forces of attraction (permanent dipoledipole interactions) between oppositely charged ions intermolecular van der Waals forces of attraction (permanent dipoledipole interactions)

(f) *

SiCl4

covalent

simple molecular

(g) *

Ar

simple molecular

(h) *

C
graphite

covalent

giant molecular layered simple molecular

(i) *

HCl

covalent

(j)

P4

covalent

simple molecular

(k) (l)

CH3OH covalent

simple molecular simple molecular

CH3F

covalent

(m)*

FeSO4

ionic covalent

giant ionic simple molecular

(n) * (CH3)3N

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*10 (a)

Aluminium fluoride (m.p. = 1291oC) and phosphorous trifluoride (m.p. = 151oC) have very different physical properties. Draw the dotandcross diagrams to illustrate the bonding of these compounds, and hence explain the difference in their melting points in terms of chemical bonding and structure.

Aluminium fluoride

3+

Al

has a giant ionic structure It has a high melting point as a large amount of energy is needed to overcome the strong electrostatic forces of attraction between oppositely charged ions during melting Phosphorus trifluoride

P F

has a simple molecular structure It has a low melting point as a small amount of energy is needed to overcome the weak intermolecular van der Waals forces of attraction during melting

23

10(b) Suggest one further physical property in which they might differ, specifying the difference in the property.

Aluminium fluoride is expected to be a good conductor of electricity in the molten or aqueous state but not phosphorus trifluoride
(c) A 0.450 g sample of gaseous aluminium chloride takes up a volume of 51.2 cm3 at a temperature of 100oC and a pressure of 1.02 105 Pa. By applying the ideal gas equation, what do these data suggest about the molecular state of aluminium chloride at this temperature? Draw the suggested structure.

(c) Using pV =

mRT M

M = 1.02 10 5 51.2 10 6 = 267 g mol1

0.450 8.31 373

Aluminium chloride has an apparent Mr which is twice its expected theoretical Mr of 133.5 exists as dimers through dative bonds under the given conditions

Cl Al Cl

Cl Al Cl

Cl Cl

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*11 (a)

Nitrogen and boron combine to form boron nitride, with empirical formula BN, which has a graphite like structure. Draw the structure of boron nitride in which the boron and nitrogen atoms alternate in a graphite like structure.

Boron nitride has graphitelike structure with alternate B and N atoms.

B B N B N N B N N B

N B

B B N

Only need to draw 2 plates per layer (Those i

N N B N B B N

B N B

B N

N N B

(b)

By considering the electron distribution of your above structure, suggest with reasoning the likely electrical conductivity of boron nitride.

nonconductor of electricity when perpendicular and parallel to layers: absence of free mobile ions or delocalised electrons to conduct electricity Note: Lone pair electrons on N are not able to delocalise due to high electronegativity. Hence cannot conduct electricity. Compared to graphite, the non-bonding electrons of C in graphite can delocalise, hence able to conduct electricity parallel to layers.
(c) Suggest one probable industrial application of boron nitride.

It could be used as a machinery lubricant.

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12 (a)*

Explain each of the following observations as fully as you can in terms of chemical bonding and structure: ammonia has a higher boiling point than phosphine (PH3)

Phosphine has a simple molecular structure It has a low boiling point as a small amount of energy is needed to overcome the weak intermolecular van der Waals forces of attraction during boiling Ammonia has a simple molecular structure It has a higher boiling point as a larger amount of energy is needed to overcome the relatively stronger intermolecular hydrogen bonds during boiling
(b) diamond is a poor conductor of electricity but not graphite

Diamond has a giant molecular structure nonconductor of electricity: absence of free mobile ions or delocalised electrons to conduct electricity Graphite has a giant molecular layered structure nonconductor of electricity when perpendicular to layers: absence of free mobile ions or delocalised electrons to conduct electricity good conductor of electricity when parallel to layers: the nonbonding valence electrons of the carbon atoms are delocalised over each plane of layers to conduct electricity
(c)* aluminium conducts electricity both in the solid and liquid states

Aluminium has a giant metallic structure

26

 good conductor of electricity in both solid and liquid states: presence of delocalised electrons which are free and mobile to conduct electricity
(d) lithium fluoride (LiF) is a nonconducting solid at room temperature which can undergo melting to form a liquid that conducts electricity

Lithium fluoride has a giant ionic structure nonconductor of electricity in solid state: ions can only vibrate about fixed positions and are not mobile to conduct electricity good conductor of electricity in molten state: presence of free mobile ions to conduct electricity
(e)* sodium chloride is brittle but sodium is malleable

Sodium chloride has a giant ionic structure brittle: a stress applied on an ionic lattice causes sliding of layers of ions; ions of similar charges come together and resultant repulsion shatters the ionic structure Sodium has a giant metallic structure malleable (i.e. easily bent): a stress applied on a metallic lattice causes mere sliding of layers of cations in a sea of delocalised electrons without breaking the metallic bonds; the lattice structure is not shattered

27

(f)

carbon dioxide is a gas at room temperature but silicon dioxide is a solid with high melting point

Carbon dioxide has a simple molecular structure has a low boiling point as a small amount of energy is needed to overcome the weak intermolecular van der Waals forces of attraction (temporary dipole-dipole interactions) during boiling, so exists as a gas at room temperature At room temperature, there is sufficient energy to overcome these intermolecular forces. Silicon dioxide has a giant molecular structure has a high melting point: a large amount of energy is needed to overcome the strong covalent bonds between atoms in a giant extensive network during melting At room temperature, there is insufficient energy to overcome these bonds.
(g)* ethanol (CH3CH2OH) is miscible in water but bromoethane (CH3CH2Br) is not

Ethanol has a simple molecular structure soluble in water: favourable hydrogen bonds between ethanol and water molecules are formed in the solvation process Bromoethane has a simple molecular structure with intermolecular van der Waals forces of attraction insoluble in water: no favourable interactions between bromoethane and water molecules can be formed as the weak intermolecular van der Waals forces of attraction in
28

bromoethane are not able to displace the strong intermolecular hydrogen bonds in water for solvation/hydration to occur
(h)* butane (CH3CH2CH2CH3) has a higher boiling point than 2methylpropane (CH(CH3)3)

Both compounds are simple molecular with intermolecular van der Waals forces of attraction Butane is a straight chain alkane while 2methylpropane has a branched chain However, Extent of surface area of contact:: Butane > 2methylpropane Strength of intermolecular forces of attraction: Butane > 2methylpropane Energy required to overcome these forces: Butane > 2methylpropane Hence, boiling point of butane is higher than that of 2methylpropane

29

(i)

butane (CH3CH2CH2CH3) has a lower boiling point than butanol (CH3CH2CH2CH2OH)

Butane has a simple molecular structure has a low boiling point as a small amount of energy is needed to overcome the weak intermolecular van der Waals forces of attraction (temporary dipole-dipole interactions) during boiling Butanol has a simple molecular structure has a higher boiling point as a larger amount of energy is needed to overcome the relatively stronger intermolecular hydrogen bonds during boiling
*13 Explain each of the following observations on physical property in terms of chemical bonding and structure:

(a)

Substance methanol (CH3OH) sodium chloride Iodine

Solubility in water soluble soluble insoluble

Methanol has a simple molecular structure soluble in water: favourable hydrogen bonds between methanol and water molecules are formed in the solvation process Sodium chloride has a giant ionic structure soluble in water: favourable iondipole interactions between ions and water molecules are formed and this process releases energy which facilitates the detachment of ions from the ionic lattice for hydration to occur

30

Iodine has a simple molecular structure insoluble in water: no favourable interactions between iodine and water molecules can be formed as the weak intermolecular van der Waals forces of attraction in iodine are not able to displace the strong intermolecular hydrogen bonds in water for solvation to occur
13(b)
Substance copper magnesium chloride phosphorous silicon carbide (SiC) Electrical conductivity high nil in solid state high in molten state nil nil

Copper has a giant metallic structure good conductor of electricity in both solid and liquid states: presence of delocalised electrons which are free and mobile to conduct electricity Magnesium chloride has a giant ionic structure nonconductor of electricity in solid state: ions can only vibrate about fixed positions and are not mobile to conduct electricity good conductor of electricity in molten state: ions are free and mobile to conduct electricity Phosphorus has a simple molecular structure nonconductor of electricity: absence of free mobile ions or delocalised electrons to conduct electricity Silicon carbide has a giant molecular structure nonconductor of electricity: absence of free mobile ions or delocalised electrons to conduct electricity
31

*14

A student commented that sodium chloride (NaCl) has a very high melting point while tetrachloromethane (CCl4) boils below 100 C, so ionic bonds are much stronger than covalent bonds.

Comment on the validity of the above statement using your knowledge of chemical bonding and structure.

Sodium chloride has a giant ionic structure has a high melting point: a large amount of energy is needed to overcome the strong ionic bonds (electrostatic forces of attraction between oppositely charged ions) during melting Tetrachloromethane has a simple molecular structure has a low boiling point: a small amount of energy is needed to overcome the weak intermolecular van der Waals forces of attraction during boiling boiling a simple molecular substance does not involve supplying energy to overcome the covalent bonds between atoms within the molecules, so the comment that ionic bonds are much stronger than covalent bonds is invalid

32

*15

With reference to the type and extent of relevant intermolecular forces, explain as fully as you can the expected order of the following substances in increasing boiling point: hydrogen (H2), fluorine (F2), hydrogen fluoride (HF), sodium fluoride (NaF) and chlorofluoride (ClF).

Hydrogen, fluorine have simple molecular structures with weak intermolecular van der Waals forces of attraction due to temporary dipole-dipole interactions However, Relative molecular mass and hence no. of electrons:H2 < F2 Strength of intermolecular forces of attraction: H2 < F2 Energy required to overcome these forces: H2 < F2 chlorofluoride Has a simple molecular structure with stronger intermolecular van der Waals forces of attraction due to permanent dipole-dipole interactions Large amount of energy is thus needed during boiling Hydrogen fluoride has a simple molecular structure with relatively stronger intermolecular hydrogen bonds Larger amount of energy is needed during boiling Sodium fluoride has a giant ionic structure has the highest boiling point: a very large amount of energy is needed to overcome the very strong ionic bonds (electrostatic forces of attraction between oppositely charged ions) during boiling Expected order in increasing boiling point: H2 < F2 < ClF < HF < NaF
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*16

The equation below shows the reaction between boron trifluoride and a fluoride ion. BF3 + F BF4 Draw diagrams to show the shape of the BF3 molecule and the shape of the BF4ion. In each case, name the shape. Account for the shape of the BF4 ion and state the bond angle present.

(a)

F B F
Trigonal planar

F
F

B F F

Tetrahedral

For BF4 There are 4 bond pairs and 0 lone pair around B To minimise repulsion, the 4 electron pairs are directed to the corners of a tetrahedron BF4- has a bond angle of 109.5
(b) In terms of the electrons involved, explain how the bond between the BF3 molecule and the F ion is formed. Name the type of bond formed in this reaction.

F B F

B atom in BF3 is electron-deficient (only 6 electrons around it), hence it accepts one lone pair electrons from F ion via a dative bond and thus achieve stable octet configuration

34

MultipleChoice Questions

1.

2.

3.

4.

5.

6.

7.

35

8.

9.

10.

11.

12.

13.

14.

15.

36

16.

17.

18.

19.

20.

21.

22.

Answers : 1 2 3 D B D

4 A

5 A

6 B

7 D

8 D

9 D

10 D

11 D

12 B

13 C

14 A

15 D

16 D

17 D

18 C

19 C

20 D

21 A

22 C

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