1

Chapter 15

Group 15 ElementsOccurrence and extraction

Physical Properties

Metals

Halides oxides hydroxides salts of oxoacids

Phosphoacids

Sulfides and selenides

2

httpwwwcpscgovPageFiles122137270pdf

Relative abundances of the group 15 elements in the Earthrsquos crust

The main components (by percentage volume) of the Earthrsquos atmosphere

httpwwwsemiconductor-todaycomnews_items2012APRILYOLE_170412html

2

httpwwwcpscgovPageFiles122137270pdf

Relative abundances of the group 15 elements in the Earthrsquos crust

The main components (by percentage volume) of the Earthrsquos atmosphere

httpwwwsemiconductor-todaycomnews_items2012APRILYOLE_170412html

3

Phosphorus containing nerve agents

Destruction of the nerve agents

Selected low-temperature baths involving liquid N2

4

covalent bond enthalpy terms (kJ mol1)

vs

5

Schematic representation of the electronic repulsion believed to weaken the FF bond in F2

N2 - dinitrogen

httpwwwbbccoukschoolsgcsebitesizescienceedexcel_pre_2011oneearthusefulproductsrev2shtml

Fractional distillation

httpwwwmvsenggcomproductsnitrogenmembranenitrogenmembrane_process_detail

Membrane separation

Composition of air

Methods to produce N2 on a small scale

4

covalent bond enthalpy terms (kJ mol1)

vs

5

Schematic representation of the electronic repulsion believed to weaken the FF bond in F2

N2 - dinitrogen

httpwwwbbccoukschoolsgcsebitesizescienceedexcel_pre_2011oneearthusefulproductsrev2shtml

Fractional distillation

httpwwwmvsenggcomproductsnitrogenmembranenitrogenmembrane_process_detail

Membrane separation

Composition of air

Methods to produce N2 on a small scale

5

Schematic representation of the electronic repulsion believed to weaken the FF bond in F2

N2 - dinitrogen

httpwwwbbccoukschoolsgcsebitesizescienceedexcel_pre_2011oneearthusefulproductsrev2shtml

Fractional distillation

httpwwwmvsenggcomproductsnitrogenmembranenitrogenmembrane_process_detail

Membrane separation

Composition of air

Methods to produce N2 on a small scale

6

tetrahedral P4

Part of one of the chain-like arrays of atoms present in the infinite lattice of Hittorfrsquosphosphorus

Part of one layer of puckered 6-membered rings present in black phosphorus

httpenwikipediaorgwikiFilePhosphCombyjpg

httpenwikipediaorgwikiFilePhosphorusAllotropessvg

Phosphorus

ArsenicArsenic antimony and bismuth in the solid state

Vapor phase

4M + 3O2 2M2O3 (M = As Sb Bi)

2As + 6NaOH 2Na3AsO3 + 3H2

7

httpwwwyettercocommedia-libraryvideospreview12jpg

8

Chemistry of ammonia (NH3)

barrier to inversion is low 24 kJ mol-1

4NH3 + 3O2 2N2 + 6H2

4NH3 + 5O2 ndashndashPtRh 4NO + 6H2O

NH3(aq) + H2O(l) [NH4]+(aq) + [OH]-(aq) Kb = 18x10-5

[NH4]+(aq) + H2O(l) [H3O]+(aq) + NH3(aq) Ka = 56x10-10

NH3 + HBr NH4Br

CaSO4 + 2NH3 + CO2 + H2O CaCO3 + [NH4]2SO4

NH3 + HNO3 NH4NO3

Oxidation products depend on conditions

Chemistry of phosphinephosphane (PH3)

K + PH3 K+ + [PH2]- + 12H2

HX + PH3 PH4X

[PH4]+ + H2O PH3 + [H3O]+

PH3 acts as a Lewis base forms a range of adducts

H3BmiddotPH3Cl3BmiddotPH3 Ni(PH3)4 Ni(PH3)2(CO)2

PH3 + 2O2 --Δ H3PO4

liquid NH3

9

Hydrides E2H4 (E = N P As)

(a) The structure of N2H4 and Newman projections showing (b) the observed gauche conformation and (c) the possible staggered conformation An eclipsed conformation is also possible

NH3 + NaOCl NH2Cl + NaOH fast

NH3 + NH2Cl + NaOH N2H4 + NaCl + H2O slow

Hydrazine (N2H4) is kinetically stable with respect to N2 and H2 ΔfH(298K) = +506 kJ mol-1

Removes O2 from industrial boilers (forms N2H4 + O2 N2 + 2H2O)

Alkyl derivatives used with N2O4 as rocket fuel

High Energy Density Materials

55-azotetrazolate dianion

[N2H5]2(2+) 2H2OBa2+ + [N2H5]2[SO4]

373 K in vacuo

ΔfH(s 298 K) = +858 kJmol(37 kJg)

[N2H5]2(2+)[N2H5]2

(2+) 2H2O

10

[P3H3]2-

Potential diagram for nitrogen at pH = 0

Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element

Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+

11

HN3

[N3]

[N3HN3]

[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt

12

trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-

Metal and non-metal azide compounds

N2 isolated 1790N3

- synthesized 1890N5

+ synthesized 1999

[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K

[N5]+[SbF6]-

[NO]+[SbF6]- + 25N2

[NO2]+[SbF6]- + 25N2

[Br2]+[SbF6]- + 25N2

NO

NO2

Br2

13

Nitrides

Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN

bullHydrolysis of saline hydrides liberates NH3

bullNa3N is hygroscopic

Na3N + 3H2O 3NaOH + NH3

bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities

Pernitrides [N2]2- are known for Sr Ba

bullConditions of 5600 bar of N2 at 920 K for BaN2

Si3N4 are used in glow plugs

titanium nitride coated saw blades

Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures

bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages

Phosphides

bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities

bull Group 1 metals form M3P and Group 2 metals form M3P2

bull Are hydrolyzed by water and can be considered ionic

httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract

9

Hydrides E2H4 (E = N P As)

(a) The structure of N2H4 and Newman projections showing (b) the observed gauche conformation and (c) the possible staggered conformation An eclipsed conformation is also possible

NH3 + NaOCl NH2Cl + NaOH fast

NH3 + NH2Cl + NaOH N2H4 + NaCl + H2O slow

Hydrazine (N2H4) is kinetically stable with respect to N2 and H2 ΔfH(298K) = +506 kJ mol-1

Removes O2 from industrial boilers (forms N2H4 + O2 N2 + 2H2O)

Alkyl derivatives used with N2O4 as rocket fuel

High Energy Density Materials

55-azotetrazolate dianion

[N2H5]2(2+) 2H2OBa2+ + [N2H5]2[SO4]

373 K in vacuo

ΔfH(s 298 K) = +858 kJmol(37 kJg)

[N2H5]2(2+)[N2H5]2

(2+) 2H2O

10

[P3H3]2-

Potential diagram for nitrogen at pH = 0

Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element

Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+

11

HN3

[N3]

[N3HN3]

[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt

12

trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-

Metal and non-metal azide compounds

N2 isolated 1790N3

- synthesized 1890N5

+ synthesized 1999

[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K

[N5]+[SbF6]-

[NO]+[SbF6]- + 25N2

[NO2]+[SbF6]- + 25N2

[Br2]+[SbF6]- + 25N2

NO

NO2

Br2

13

Nitrides

Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN

bullHydrolysis of saline hydrides liberates NH3

bullNa3N is hygroscopic

Na3N + 3H2O 3NaOH + NH3

bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities

Pernitrides [N2]2- are known for Sr Ba

bullConditions of 5600 bar of N2 at 920 K for BaN2

Si3N4 are used in glow plugs

titanium nitride coated saw blades

Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures

bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages

Phosphides

bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities

bull Group 1 metals form M3P and Group 2 metals form M3P2

bull Are hydrolyzed by water and can be considered ionic

httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract

10

[P3H3]2-

Potential diagram for nitrogen at pH = 0

Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element

Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+

11

HN3

[N3]

[N3HN3]

[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt

12

trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-

Metal and non-metal azide compounds

N2 isolated 1790N3

- synthesized 1890N5

+ synthesized 1999

[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K

[N5]+[SbF6]-

[NO]+[SbF6]- + 25N2

[NO2]+[SbF6]- + 25N2

[Br2]+[SbF6]- + 25N2

NO

NO2

Br2

13

Nitrides

Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN

bullHydrolysis of saline hydrides liberates NH3

bullNa3N is hygroscopic

Na3N + 3H2O 3NaOH + NH3

bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities

Pernitrides [N2]2- are known for Sr Ba

bullConditions of 5600 bar of N2 at 920 K for BaN2

Si3N4 are used in glow plugs

titanium nitride coated saw blades

Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures

bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages

Phosphides

bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities

bull Group 1 metals form M3P and Group 2 metals form M3P2

bull Are hydrolyzed by water and can be considered ionic

httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract

11

HN3

[N3]

[N3HN3]

[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt

12

trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-

Metal and non-metal azide compounds

N2 isolated 1790N3

- synthesized 1890N5

+ synthesized 1999

[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K

[N5]+[SbF6]-

[NO]+[SbF6]- + 25N2

[NO2]+[SbF6]- + 25N2

[Br2]+[SbF6]- + 25N2

NO

NO2

Br2

13

Nitrides

Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN

bullHydrolysis of saline hydrides liberates NH3

bullNa3N is hygroscopic

Na3N + 3H2O 3NaOH + NH3

bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities

Pernitrides [N2]2- are known for Sr Ba

bullConditions of 5600 bar of N2 at 920 K for BaN2

Si3N4 are used in glow plugs

titanium nitride coated saw blades

Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures

bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages

Phosphides

bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities

bull Group 1 metals form M3P and Group 2 metals form M3P2

bull Are hydrolyzed by water and can be considered ionic

httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract

12

trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-

Metal and non-metal azide compounds

N2 isolated 1790N3

- synthesized 1890N5

+ synthesized 1999

[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K

[N5]+[SbF6]-

[NO]+[SbF6]- + 25N2

[NO2]+[SbF6]- + 25N2

[Br2]+[SbF6]- + 25N2

NO

NO2

Br2

13

Nitrides

Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN

bullHydrolysis of saline hydrides liberates NH3

bullNa3N is hygroscopic

Na3N + 3H2O 3NaOH + NH3

bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities

Pernitrides [N2]2- are known for Sr Ba

bullConditions of 5600 bar of N2 at 920 K for BaN2

Si3N4 are used in glow plugs

titanium nitride coated saw blades

Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures

bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages

Phosphides

bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities

bull Group 1 metals form M3P and Group 2 metals form M3P2

bull Are hydrolyzed by water and can be considered ionic

httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract

13

Nitrides

Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN

bullHydrolysis of saline hydrides liberates NH3

bullNa3N is hygroscopic

Na3N + 3H2O 3NaOH + NH3

bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities

Pernitrides [N2]2- are known for Sr Ba

bullConditions of 5600 bar of N2 at 920 K for BaN2

Si3N4 are used in glow plugs

titanium nitride coated saw blades

Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures

bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages

Phosphides

bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities

bull Group 1 metals form M3P and Group 2 metals form M3P2

bull Are hydrolyzed by water and can be considered ionic

httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract

14

Gallium Arsenide

bull Important group III-V semiconductor that crystallizes with zinc-blende structure

bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region

bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1

bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity

bull Highest-efficiency single-junction solar cell at 288

bull httpdxdoiorg1011092FPVSC20126317891

Unit cell of NiAs

Ni

As

NiAs (nickel arsenide)

15

[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of

[PdBi10]4

16

Selected reactions of PCl5

SbF54

[Sb2F11] [As6I8]2

17

[BiCl3(15-crown-5)] [BiCl3L]

Oxides of Nitrogen

18

[N2O2]2-

19

HNO3

NO3-

20

oxoacids of phosphorus

21

[W3(OH2)9NiSe4PH(OH)2]4

22

enantiomers (non-superimposable mirror images)

unit cell of FeSb2O6 unit cell of NaSbO3

23

[Cl3PNPCl2NPCl3]

[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3

phosphazenes (NPX2)3 P4N4 ring conformations

P+

P+

P+N-

N-

N-

24

(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2

16

Selected reactions of PCl5

SbF54

[Sb2F11] [As6I8]2

17

[BiCl3(15-crown-5)] [BiCl3L]

Oxides of Nitrogen

18

[N2O2]2-

19

HNO3

NO3-

20

oxoacids of phosphorus

21

[W3(OH2)9NiSe4PH(OH)2]4

22

enantiomers (non-superimposable mirror images)

unit cell of FeSb2O6 unit cell of NaSbO3

23

[Cl3PNPCl2NPCl3]

[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3

phosphazenes (NPX2)3 P4N4 ring conformations

P+

P+

P+N-

N-

N-

24

(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2

17

[BiCl3(15-crown-5)] [BiCl3L]

Oxides of Nitrogen

18

[N2O2]2-

19

HNO3

NO3-

20

oxoacids of phosphorus

21

[W3(OH2)9NiSe4PH(OH)2]4

22

enantiomers (non-superimposable mirror images)

unit cell of FeSb2O6 unit cell of NaSbO3

23

[Cl3PNPCl2NPCl3]

[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3

phosphazenes (NPX2)3 P4N4 ring conformations

P+

P+

P+N-

N-

N-

24

(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2

18

[N2O2]2-

19

HNO3

NO3-

20

oxoacids of phosphorus

21

[W3(OH2)9NiSe4PH(OH)2]4

22

enantiomers (non-superimposable mirror images)

unit cell of FeSb2O6 unit cell of NaSbO3

23

[Cl3PNPCl2NPCl3]

[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3

phosphazenes (NPX2)3 P4N4 ring conformations

P+

P+

P+N-

N-

N-

24

(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2

19

HNO3

NO3-

20

oxoacids of phosphorus

21

[W3(OH2)9NiSe4PH(OH)2]4

22

enantiomers (non-superimposable mirror images)

unit cell of FeSb2O6 unit cell of NaSbO3

23

[Cl3PNPCl2NPCl3]

[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3

phosphazenes (NPX2)3 P4N4 ring conformations

P+

P+

P+N-

N-

N-

24

(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2

20

oxoacids of phosphorus

21

[W3(OH2)9NiSe4PH(OH)2]4

22

enantiomers (non-superimposable mirror images)

unit cell of FeSb2O6 unit cell of NaSbO3

23

[Cl3PNPCl2NPCl3]

[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3

phosphazenes (NPX2)3 P4N4 ring conformations

P+

P+

P+N-

N-

N-

24

(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2

21

[W3(OH2)9NiSe4PH(OH)2]4

22

enantiomers (non-superimposable mirror images)

unit cell of FeSb2O6 unit cell of NaSbO3

23

[Cl3PNPCl2NPCl3]

[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3

phosphazenes (NPX2)3 P4N4 ring conformations

P+

P+

P+N-

N-

N-

24

(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2

22

enantiomers (non-superimposable mirror images)

unit cell of FeSb2O6 unit cell of NaSbO3

23

[Cl3PNPCl2NPCl3]

[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3

phosphazenes (NPX2)3 P4N4 ring conformations

P+

P+

P+N-

N-

N-

24

(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2

23

[Cl3PNPCl2NPCl3]

[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3

phosphazenes (NPX2)3 P4N4 ring conformations

P+

P+

P+N-

N-

N-

24

(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2

24

(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2