PHOSPHORUS
2ë
3ë*
References
1ë
1+
3+
2+
>0
;C
u
(+
Phosphides M3Px
Covalent
43.1
5
É.
wh. (a
)
P, Pa 10
wh. ( b
)
ììììì
* See notes to p. 58.
40
589
t , C
P
O
O
2 SO
4
H
H2O
(H+, t)
OH
;B
a(
OH
)2 (
PH
3"
)
P
O
O
P
PCl3 ( P); Hg2+
H+ (cation exchanger)
M[H2PO2] n, hypophosphites
NaH2PO2 H2O 19)
KH2PO2; NH4H2PO2
Mg(H2PO2)2 6 H2O
Ba(H2PO2)2 H2O
Ca(H2PO2)2, readily sol. in H2O
O
[cf. CaHPO4 and
Ca3(PO4)2],
anion: distort.
H P O
tetrahedron,
P ì O 1.52
H
P
O
P
O
PBr3
! PH3 + H3PO3,
v. strong Red agent (in conc.
19)
soln. only, t)
M
P
O
M2[H2P2O5], pyrophosphites
Na2H2P2O5; ZnH2P2O5,
anion: 2 tetrahedra with com11)
mon vertex
2
O
O
SO
H3PO2 = H[H2PO2], hypophosphorous ac., cr., colrl., hyg.,
m.p. 27, K=10 1,
sol. in alc., eth.;
cub., struct. analogue of Po,
a = 2.38, d = 3.83
2)
P
6
O
Mn2H11P5O15 4 H2O
MnH10P4O12 H2O
Mn3H6P4O12 1.5 H2O 16)
PCl3 ( H2O)
(
P
O
O
O
M6P6O12 n H2O, M = Rb, Cs, Ba/2,
hexametaphosphites, anion: chair 31)
2
H
2.18
P, wh.
P
H
")
H2
Region of sld. P red
PÂ
Tetraphosphorus complexes
[MCl(P4)(PR3)2], M = Rh, Ir
P
O
H4P2O5 = H2[H2P2O5], di(pyro)phosphorous ac.,
needles, colrl., m.p. 38, dec. 130
H4P2O4=H2[H2P2O4]
H
,
280
23)
50
P, met., rhombohedral, As-type
struct., a = 3.52, a = 57.4,
P ì P 2.38, d = 3.56,
5
O
H2O
Ba[H2P2O4] #
O O
PÂ
# 124000 10
O
O
P2I4
H[OPH(O) ì PH2]
H
(O
44
Phase Diagram of P
[P8] 2+(HSO3F)2ë
[P4] 2+(HSO4)2ë,
colrl. (known only
in soln.),
[P8] 2+, bl.,
[P4] 2+, colrl.,
diamagn. ions 3)
O
H2
77
# 8300010
MOCl+MOH
H2O
2
O 2(
)3
R3
0.18
Pn, blk., subl. 453,
m.p. 1000 /18 108 PÂ,
d=2.69, thermodynamically
stab., non-react., inê. 400 ,
(a = 3.31, b = 4.38, c = 10.50) ë
corrugated layers in rhomb. struct.,
P ì P 2.18, € PPP 99, graphite-like
semiconductor
5
!
. , lu
PO
2)
l(P
ur
po
va
.P
red P vapour
wh
1
rea
ain
, ch
0
550
MC
wh.+liq.
n
ctio
O
3
}
}
)
(p
Liq., P4
00
6
cool. 280
Pn, red, insol. in CS2, nontoxic, t
Gas
inê. 240 , subl. 429,
ƒƒƒ! P
ƒƒƒ!
P4 1000
d = 2.2 ë 2.4, mol.: chains of
2 2000 P
[P:P],
various lenghts, P CN 3,
P ì P 1.90,
P ì P 2.24, € PPP 102
el. analogue of N2
450 #
Hittorf phosphorus,
6 modiécations (tricl., tetrag.,
cub.), struct.: chains of P8 grs.,
struct. analogues of As4 S4 ,
P ì P 2.22, € PPP 101
O
O
HC
Na (0 )
Metal-like
m.p.
BP#, dec. >2000, does not sol. in Ti3P
Li3P; Na3P; Na2P5 (m.p. 650)
ì
K2P5; Ba[P5]2; Rb4[P6], struct.: [P5] ac. and alk., diamond-like struct. TiP 1580 with dec., struct.: NaCl type
and [P6] planar rings, P ì P 2.20
AlP, dec. 2000,
sphaleriteCr3P ì
Na3P21; Ba3[P7]2, anion: cluster
CrP 1600
like
+ H2O ! PH3
Fe3P 1200 with decomp.
K4P3; K5P4, anions: chains
InP#, dec. 1070
struct.
Mg3P2; Ca3P2 +O2 ë inê.,
Fe2P 1356
GaP#, m.p. 1467
(ZnS)
Zn3P2; Cd3P2 +H2O ! PH3+... AsP#, dec. 750
FeP
ì ferromagn.
Cu3P#; CuP2#, insol. in HNO3 (t) ScP; YP; LaP, struct.: NaCl type FeP2 ì
HO
UP; U3P4
LnP + H2O ! PH3 + . . .
P(HgCl)3# 2 PH3 + HgCl2
Rh2P ; Ir2P, anti-CaF2 type struct.
Conductors (TiP) or semiconducDielectrics or semiconductors
tors (CrP); chem. inert (activity
(M = Mg, Ca, Zn, In, Ga, As)
raises with decreasing P content);
KZnP, CaZn2P2, struct.: layers of
sol. in Na2O2 melts
[ZnP4/4] tetrahedra Zn ì P 2.49 22)
[P7]3 ë
Salt-like
250 , p>5 107 Pa
(I2; Na; hv-UV, X-ray)
P 1.65
2.20
CO
)
)
3
O
O
O
O
P
P
O
H
H
O
3
M3[HP2O5],
O diphosphites
Na3HP2O5 12 H2O
H3PO3=H2[HPO3], phosphorous ac., cr., colrl.,
hyg., m.p. 74, dec. 200, K1=10 2, K2=10 7,
sol. in H2O, alc.; mol.: distort. tetrahedron;
t
H3PO3 (cr.) ! PH3+H3PO4 ; strong Red agent
(<H3PO2; reacts slowly, t), at 20 not reacts with
HNO3
O 11 1.54
H2[HPO3] > P(OH)3; O
6
H1.39P
OH
P(OR)3 ! (RO)2P
2
(RHal)
R
10
OH
(Arbuzov rearrangement)
t ( H2O)
(t)
2
Ag
+;
O
H2
PO
3
ëH
99
O
P2O3, phosphorous anhydride, cr., wh., m.p. 24,
b.p. 175, DH ˆ 1640 (for P4O6), sol. in org. solvs.
In gas, solns and one of modiécations: P4O6 dimers.
In mol.: 4 c-tetrahedra [:PO3], bounded by common
vertices, forming "large tetrahedron" [P4]. In other
modiécations: polymers of [PO4] tetrahedra
)
+
M
HCl
(t)
C
P
P
nce
esce
min
Ca3(PO4)2
")
CO
3
O
125
1.47
Ca+I 2
O
aSi
(
C
15)
Ca2PI; Ca3PI3, struct.: cation vacancies, octahedra
[CaP3I3] and [CaP2I4],
Ca ì P 2.83, Ca ì I 3.41
and 3.27 12)
2.1
;
ol.
M; M2On; MHaln(g.)
PH3)
Na2PH
MAI(PH2)4; SiF3(PH2)
;
44
1)
# 100 vac. (
;
E.N.
3d
P4, wh., soft, waxy
(yel. due to Pred and As impurities),
m.p. 44, b.p. 257, sol. in CS2, NH3,
0
150
(
SO2, toxic, inê. 40 .
2
SiO
Struct.: mol. P4 ë tetrahedron,
C+
P ì P 2.21, € PPP 60, P CN 3.
Strain in the tetrahedron is responS2O6F2 (HSO3F);
sible for high reactivity of P.
a-, cub., a=18.51, d=1.83
H2S2O7 ( SO2 H2SO4)
# < 76.4
b-, tricl., a = 11.45, b = 5.50,
c=11.26, a=71.8, b=90.4, g=71.6,
d = 1.94, in [P4] P ì P 2.17 34)
2)
MPH2, dihydrophosphides,
cr., colrl., self-igniting
;:
3p
P
O
P2O5
Ca3P2
H2 (300 t( H
, p); H
Cl( P
2)
Cl3 ); M
OH(
MH P
2 O
M (liq. NH3)
3s
O
[R4N][Ru4(CO)12(m3-PO),
38)
cr., stab.
P4O, polymer
co
Phosphonium salts [PH4]X
cr., colrl.
[PH4]ClO4, expl.
PH4Hal >
PH3+HHal (g.)
subl. t
28
PH4Cl
38
PH4Br
PH4I 80 (b.p.), 18 (m.p.)
v. strong Red agent;
+H2O ! PH3+HHal;
cation: tetrahedron (sp3 ),
P ì H 1.42
P0
H2O
PCl3
lH 4
(25 , 35 108 Pa; Hg, 370 )
OH
HX
H2O
LiA
H2O ë cool (v. slowly)
H+
+
PH+
4 +H2O . PH3+H2O > H3O +PH2
29
29
K=10
K=10
v. weak donor
PR3, strong donors
[Ni(PH3)4]; [Co(N2)(PR3)3]
(PH)n, solid,
yel., does not
react with ac.
and alk.;
400
! P4+PH3
H2SO4
P2H4, diphosphine, liq., colrl., m.p. ë 99,
b.p. 63, struct. analogue of N2H4, P ì P
2.22, P ì H 1.45, € HPH 94 and 99,
dihedral € 74 (trans- and gauche- isomers), inê. at 20 (as impurity in PH3),
does not react with ac.;
n H2O, clathrate 15)
2.21
PH3, phosphine, gas, colrl., toxic, evil-smelling,
m.p. 134, b.p. 88, inê. 150 , DH=+5,
v. strong Red agent, sol. in H2O 20 vol %, m = 0.58;
mol.: trig. pyramid, P ì H 1.42, € HPH 93 (p3);
5.75 H2O (8 : 46), clathrate
H2O
PCl3
MH[HPO3], hydrogen phosphites
NaH2PO3, 2.5 H2O, m.p. 42, dec. 100
KH2PO3; Zn(H2PO3)2, anion: distort.
tetrahedron, P ì O 1.51 11)
M2[HPO3], phosphites
Na2HPO3 5 H2O, m.p. 53, dec. 120
K2HPO3; MgHPO3 6 H2O
31)
Ag2HPO3#, wh.; CaHPO3#; CrHPO3 2 H2O,
t
! M3PO4 + PH3 + P + . . .
[HPO3]2 ë distort. tetrahedron, P ì O 1.52, P ì H 1.29
(NH4)3[P(Mo6O21)] 10 H2O#, yel.