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ATextBookofInorganicChemistry 10002463 PDF
ATextBookofInorganicChemistry 10002463 PDF
BY
DR . A . F . D O LLE M A N ,
Professor O rdin ar i u s in
‘
t h e Un iv er si t y O f A m st er da m ; E m er it us Professm
O rd in ar ius in t h e Un iver s it y of G r on in ge n , N et h er l an ds . and
I SS UE D IN E NG L I S H IN C OO P E RA T I O N T
WI H
H ER M O N C H A R L E S C OO P ER .
FO UR TH E N GL I SH E DI TI O N C O IM PL E TE L Y
'
TO TA L I SSU E , SI XT E E N T H OU S A N D .
N EW Y O R K
JO HN WI LEY SO N S,
L O ND O N : C HA PM S N HA LL ,
1913
?0 5 3 H ‘
C o p y r ig h t , 1 9 0 1 , 1 9 02 , 1 9 05 , 1 9 08 , 1 9 1 1 ,
BY
H ERMON C . C OO PE R .
Firs t . Se c o n d , a nd T h i d E dit i
r o n s e n t e re d at St at io n e r s
’
H all .
HQE s c m
-
mn c PR ES S
R O G ERT DRUMM O N D AN D C O MPANY
BR O O KLYN , N . Y.
PR EFA C E TO THE FO UR TH E DI TI O N .
notably those on the sulp hur oxides and acids rare gases nitroge n , ,
,
O rgani c C hem
-
ist ry
,
”
translated by WA L K E R an d M O TT .
H . C . C O O PE R .
SYRA C U S E UNI V ER S I T Y ,
O c tob er, 1 9 1 1 .
C O N TEN TS .
Lig h t -
fac e fi g ure s re fe r to p ag e s ; h e av y fa c e fi g u re s t o
-
p ar ag ra ph s .
IN TR O DU C TI O N ( 1 5) -
13 .
Hydr ogen ( I L 1 3 ) -
T H E C O N S ER V A T I O N O F M A TT ER
W a ter ( 1 5—1 9
)
Phys ic a l prop ert i es , 2 0 ; N atura l w ater, 2 0 ; C omp os it i on O f w ater, 22 .
E L E M EN TS 2 9 ; C HE M I C A L SY M B O L S AND F O R M U L AE 3 0
, ,
.
STO I C H I OM E T RI C A L CA L C U L A T I O N S
C hl orin e ( 25
C ataly t ic ct ion 3 4 ; Hyd ogen ch lorid 3 7 ; A cids b as
a , r d s lts e, ,
e s an a ,
3 9 ; C omp o s it i on O f h ydro c h l or ic a ci d 4 1 ; L aw O f G A Y L U SS A C ,
-
O zo ne ( 3 6 , 3 7 )
Formul a O f, 52 ; All otrop i sm , 5 3 .
M O L E C U L AR
WEIGH T F R OM T H E M EA S URE M EN T O F T H E D E P RE SS I O N O F
T HE F REE ZING P O INT AND E L E V A T I O N O F T H E B O I L ING P O INT ( 4 0
- -
Br om in e ( 44 ,
Hydr o en b r o g mide ,
67 .
I odine ( 46—4 8)
Hy dr og en iodide ,
71 .
D I SSOC IATI O N ( 49
Re v r ib le re ction s 7 3 ; Equilibrium 7 3 R e action ve lo city 7 5 ;
e s a , , ,
re c t io n s 7 6
a ,
.
Fl uorin e ( 52, 5 3 )
Hy dro en g fluoride 8 1 ,
.
oxygen 83 ,
.
N OM EN C L A TURE 92 .
E L E C TR O L Y TI C D I SSOC IAT I O N ( 65 66 ) ,
1 01 .
S u l p hu r ( 67 9 3 ) -
1 2 1 ; V A L EN C E 1 22 ; C ompounds O f s ulph ur w it h o xy g en
'
o gen s , , ,
l ium 1 4 8 ; T el lurium 1 50
Se en , , .
T H ER MO C HE M I S TRY (9 7—1 04 )
’
L aw Of HE SS , 1 53 : C HE M I C AL A FF INI TY , 1 56 ; T HE D I S P L A C E M ENT
OF E Q UI L IBRIU M , 1 6 0 ; PA SS I V E R E S I S TAN C E S , 1 6 1 .
N itr ogen ( 1 05
m
Th e at os ph e re , 1 6 5 ; A r gon h e lium n d compan ion e l ments 1 7 0 ; ,
a e ,
Phos phorus ( 1 3 1 “
0
A rs enic ( 1 55
Hy dr ogen r
a se n ide ,
22 3 ; H al o g e n c ompounds 226 ; ,
O xygen c o m
p o un ds 22 6 ; O xy a ci ds 2 28 ; Sulph ur c ompounds 2 2 9 ; Sulp h o
-
, , ,
salts 2 3 0 ,
.
A n tim on y ( 1 65
Hydro gen timon i de 23 2 ; H al o g e n compoun ds 23 3 ; O xygen com
‘
an , ,
p ounds ,
23 4 ; S ulphur compoun ds ,
23 6 .
C O N T E N TS . v ii
Bis m u th ( 1 7 0 1 7 4 ) -
S umm ry a O f t he n itrog en g ou p
r 23 9 .
C arbon
A llotrop ic form s , 24 1 ; M ol e cul ar an d atomic w e igh t, 2 4 6 ; C o m
po unds w i th h y dro gen , 24 8 ; C omp ou n ds w i th oxy g en , 24 9 ; O th e r
c arb on compoun ds , 2 55 ; Th e fl am e , 2 56 .
—
Silicon ( 1 90 1 96 )
Hydro g en l ci de 2 62 ; Halogen comp ou d 263 ;
Si i ,
n s, O xy g e n c om
p oun
ds , 2 6 5 ; Silicic aci ds 2 66 ; C O LL O ID S 2 6 8 , ,
.
G erm an iu m ( 1 9 7 )
Tin ( 1 98
Stan n ou s c ompou n ds ,
27 6 ; S tan n ic c omp ounds ,
27 9 .
m ry O f t h e c rb on group
a 2 87
a .
L w o f D U L O NG n d PE T I T 2 89 ; L aw f N EU M ANN 2 9 1 ; L aw o i
a a ,
o ,
«
L EN T W EIGH TS 2 9 3 ,
.
T HE PERI O DI C SY S TE M O F T H E E L E M EN TS ( 21 3 22 1 ) —
O xi des an d hydroxid es O f, 3 1 2 , Sa lt s
o f, 3 15, ( So da ,
Potass iu m —
( 22 7 23 1 )
O xygen c ompounds 3 23 ; Sa ,
lts , 3 24 .
R u bidiu m a nd C ces iu m ( 23 2)
S ummary O f t he group O f alk ali metals 330 .
A m m on iu m S a l ts ( 23 4 )
SA L SO L U I O N S 23 5—23 9
T T ( )
A C IDI M E
TRY AND A LK A LI M E TRY ( 240, 241 )
Indic ators 3 5 2 ,
.
—24
C opper ( 24 2 4)
u
C pro s o u c mpounds ,
3 55 ; C pr u ic comp ounds ,
3 58 .
Sil ver ( 24 5 24 7 )
—
C ompounds , 3 6 2 °
Ph otogr aph y, 3 64 .
G ol d ( 24 8—25 1 )
T est in g O f gold n d Silver 3 69 ; A urou s comp ounds
a , ,
3 69 A ur ic com
p ou n d 3 7 0 ; Summ ry O f t h e g ou p
s, 371 a r .
S tr on tiu m , —26 2
C al ciu m , an d B ari u m ( 2 56 )
Ca lcium , 3 76 ; O xi de s an d hydroxi de s O f, 3 7 7 ; Sa l ts O f, 3 79; G l as s ,
I
C O N TE N TS .
PA G E
3 84 ; Stront ium ,
3 86 ; Bar ium ,
3 87 ; S ummary O f t h e group Of t he
lk lin e ea th 3 88
a a r s, .
R adio -
ac tive El em en ts ( 26 7 )
Z in c ( 268 ,
269 )
C adm iu m ( 27 0)
M er cu r y ( 2 7 1
m lgam 4 1 2 ; M rcur u c ompoun d
A a s, e o s s, 4 1 3 ; M er curic compoun ds ,
E L E C TR OC HE M I S T RY ( 2 7 6
B or o n ( 2 82 ,
Ha l o g e n c mp u n d
o o s, 43 3 ; O xyg en c om pou n ds , 43 3 .
A l u m in iu m ( 284
m u
C o p o n ds O f, 43 7 .
Summ ry o f t h g up
a e ro 44 2 .
—
G rou p ( 93 299 )
C hr om iu m 2
C hr o mium mou compou d 4 50 ;
,
44 9 ; C hro s n s, mic comp ou n ds
C hr o ,
4 50 ; C h om at s 4 5 2 ; M o ly b d um 4 5 5 ;
r e , en ,
T ung t en 4 56 ; U a
s , r
n ium 4 5 7 ; Summ
,
y f t h e g o u p 4 58 ar O r , .
—
I ron ( 0 3 08)
3 2
I ron -
c b ar on sy s e t m ,
466 ; Ferro u s c o mp o u n d s, 47 3 ; Ferr ic com
po un d s, 47 4 .
C oba l t an d N i ck e l 0 —3 1 2
( 3 9 )
C ob a
47 7 ; N lt , e , 47 9 ick l .
Pl atin u m M e tal s ( 3 1 3 —3 1 6 )
R uth n ium
e ,
4 82 ; mium
Os ,
4 83 ; R h od ium ,
4 83 i ium
Ir d ,
4 84 ;
P ll dium
a a ,
4 84 ; Pl tin um
a ,
485 .
M et a l -
amm o n ia C om pou n ds . W ERNER S ’
EX TEN S I O N S OF THE N O TI O N
OF VA L EN C E (3 1 7
IN O R G A N IC C H E M I ST R Y .
INTR O D UC TI O N .
which deal with the things o n t h e ea rth and in the outside unive rse .
but sim ply the im pressions which they make upo n our sense orga n s -
.
o u r retina ; if we feel the obj ect it is not the body itself but t h e
,
excitement O f the sens ory nerves O f touch in our fingers that we are
made awar e of Hence it may be fairly asked whethe r the O bj ects
.
whether they even exist at all outside of our pe rso n The natural .
—
S ciences leave this proble m o u t O f co nsideratio n its solution is t h e
task of Speculative philoso phy In reality they are not co nce r ne d
.
the study O f the sens atio ns that we receive The se ns atio ns tak e
.
to divide the natural sciences into Zool ogy B otan y M in era l ogy , ,
and A str on om y .
Sion int o Phys ics C hem is try and B iol ogy the latte r b eing t h e s tudy
, ,
eu t ics
p .
p henomeno n When co
.
pp er is heate d in the ai r it tu r ns into a ,
"
when the phenomenon was better unde rstood b y assuming that ,
p henomena it becomes
, a t h e o ry .
PHYS I CA L A N D CHEM I CA L PHE N O M E N A .
3
int o the r eal essenc e O f things and the investigato r Very soo n ,
—
when co ppe r t o retain our forme r exampl e— is heate d in t h e
air is well kn own However the dee pe r questio n why t h e action
.
, ,
p lanets for
,
exam p le still takes place in t h e,
s ame manne r as in t h e
from the bur n ing of wood the same products ar e always O btained ;
the microsco pic st ructure O f t h e l eaves of o ne and t h e sam e plant
is neve r found to vary This general principle finds its expression
.
p r e ss u re it is fo,
r thw ith assumed that th i s m u st b e t h e case with
it m ay b e tested .
P HY S I C A L A N D C H EMI C A L P H EN O MEN A .
flame it burns with the emission of a brilliant light and turns into
,
begins to boil then distils over and condenses in the receiver The
, .
first but soon the sugar tur n s darker ; a brownish liquid distils
,
the latter ceases the wire returns to its original condition This
, .
induces an evolution O f gas and this gas arising from the wate r,
has pro perties entirely diffe rent from those of the water A lasting .
C HE MI C A L O PER ATI O N S .
.
7 I n o rd e r t o avoi d r e p etitions it seems advisa b l e at this p oin t
t o d escribe brie fly some O f the commo nest chemical o p erations .
S uol tio n — When sugar salt o r salt p etre for exam ple is pu t
.
, , ,
into water the solid substance disappears and its taste is taken
,
all pro po rtions t o im p ercep tible solubility Thus cane sugar is dis .
-
and allowed to stand two liquid layers are formed ; the water has
,
dissolved some ether and the ether some water I n most cases .
the solubility of liquids in each other also increases with the tem
p er a t u r e
. I n the case of g a s e S solubility decre ases with rising
tem perature .
o f this dilute solutio n a ain remai ns with the solid and anothe r
g
6 I N O R G A N I C C HE M I S TR Y . 7
l
is then allowed to cool the dissolved substance frequently se parates
,
FI G 1 — D I S TI L L AT I O N
. , .
former distil over and the latter remain in the distilling fl ask -
t his manner . Take for exam ple a mixture O f alcohol and water
, , .
The more volatile constituent alcohol passes over for the most , ,
Su bl im atio n — C ertain
solids e g cam phor when heated ( at
. .
,
.
,
THE EL E MEN TS .
Water is added and the whole is stirred well and gently warmed ;
after a while it is filtered and that which remains on the filter is
-
,
The undissolved part is dried and then shaken with another sol
.
can be se parated into three sub stances viz carbon sulphur and ,
.
,
s alt petre The two former are inca pable even when subj ected
.
,
remains which gives O ff red fumes on treatment with sul phuric acid ,
something that salt petre does not do Salt petre can evidently .
tain o nes that cannot be resolved into sim pler substances by our
p resent means Such .substances are called ele m e n t s A lthough .
b e found that the substances which the chem ist of t o day regards as -
“
elements have no right to the name Therefore when we use the
”
word element it is to be regarded as a relative term de pendent
,
.
,
p osed .
cause on the one hand not all the substances that possibly exist
, ,
A s may be seen fro m this list the m etal s are incl uded in the ,
stances as oxygen sul phur phosp horus et c that are cl assed under
, , , ,
.
,
the ter m n o n —
m etal s or m eta l l oids TO the l atter class bel ong .
,
combines with al most all others caus ing what is called combustion ,
.
O f t he i te ri r
n o earth o n ly a ve ry sm al l p art is kn ow n I f w e th i n k
of t he .
The following met hod for separating these gases was employed by
L A V O I S I ER in 1 7 7 4 He introduced some mercury into a retort A
.
( Fig 3 ) with a long doubly bent neck that o pened under a bell
.
,
-
F IG 3. .
—A B SO R PT I O N OF O X YGEN BY M ER C URY .
heated the reto rt steadily for several days kee ping the me r cur y ,
and the gas remaining was found t o possess other pro per t ies than
—
air it was nitrogen At the same time the mercury had been
.
t ion e d are as foll ows : Its s pecific gr avity assu ming the density
, ,
‘
O f air t o be 1 is ,
A liter O f oxygen at 0 and 7 60 mm °
.
at mm pressure Its co l or is . .
The latter is a vessel enclosed in nan air tight j acket the s pace b e -
,
~
1 oxygen
. The gas is also somewhat soluble in alcohol
.
F IG 4
. . VA C UU M Thus when the pressure becomes a fold the solu
-
,
-
' -
.
of th e p r essu r e .
This law is rigid when the solubility O f the gas is s m all ; whe n
the solubility is large for instance 1 00 volumes in l of the liquid
, ,
IO A .
mong the c h em ic a l r
p po er ties O f oxygen the most promi
nent is its vigorous suppo rt O f combustion The following are .
ul
S p hur which burns
,
in air with o nly a small flame burns in ,
with a blind ing white light steel wat ch Sp ring that has been . A -
these and analogous cases the oxygen as well as the burning mate ,
c oo ling the s c ale pan atta c hed to the m agnet Si nks I n a Similar way one
,
-
.
order to pro ve the i n c rease O f we i ght i n a c ase where only gaseo u s produc ts
are form ed a c andle m ay be b urned and the co mb ust i on produ cts
, ,
the burning of zinc ,for exam ple may be proved by heating the ,
as o x i datio n .
c ombines with them N eve rtheless the nitrogen O f the air is heated
.
,
H Y DR O GEN .
to O btain the red powder by heating pure oxygen and pure mercury
together at a lower temp erature The forme r is an exam ple of
.
HYDR O G EN .
found on the earth in the free state The gases O f some volcanoes
.
2
( ) T he acti on of zinc on dilute sul phuric acid This
is the c omm onest method .
o pened the ac i d fl ows th rough D to the m etal and the evo l ution O f hy
dro gen commences at O nce The cock being c l osed a gain the gas stil l
.
,
14 I N O R G AN I C C HE M I S TR Y M 11
(3 ) Th e ac t i on of
z in c o r aluminium fil
in gs o n caustic p otas h
o r Slaked lim e .
( ) Th e action of
4
s o d ium o r p otassium
o n wat e r or alcohol .
( 5) M a g n e s i u m
p o w d e r,
wh e n b oile d
with water ,als o
e volv e s hydrog e n ,
hydroge n ( c om par e
I I 2. Th e physica l prope rties o f hy d rog e n ar e thes e : I t is t h e
lightes t of all known su b stances its s p ecific gravity ( air = 1 )
,
O n e lite r o f hy d rogen at 0 an d
°
a mounting to only
7 6 0 mm Hg pressure weighs
. . g Its lightness renders it
.
ro
p p ert y serves for the identification of hydrogen gas
.
t ill they reach the fl ame and the poss ib ili ty of an e x pl os i on i s av o i ded
, .
F IG . 6 .
— O X Y H YDR O GEN B L O W P I P E .
, ,
heard in this case because the steam at the moment of its form a
,
°
509 for 50 minutes of the whole is changed to water N O W
, .
take 1 00 minutes till the p art of the gas had formed water .
cal reactio ns When we see that wood sul phur etc burn quickly
.
, ,
.
,
has the power to withdraw oxygen from many of its comp ounds .
will usually unite with the hydrogen to form water C o pper oxide .
a pplied ; one soo n sees the black oxide change to red co pper and ,
et c .
THE C O N SE R VA TI O N O F M A TTER .
4 The
1 .quantitative relationshi p s in oxidizing and reducing
ro cesses such as have been discussed in 1 3 i e the relatio ns
p , ,
. .
C o pper p owder for exam ple may be placed in a tube and the
, ,
led over the co pper at a high tem perature The a pparatus should .
tube with the co pper oxide and heat a pplied Here also arrange .
co pper oxide is trans formed back to co pper When the tube and .
d o to day -
F IG 7 — COM BU S T I O N
. . OF HYDR O GEN .
two necked (WOU LFF) bottle from zin c and sul phu ri c acid
-
In .
—
pumic e s to ne so aked in sul p huric acid The dry gas is ignited and
.
,
heated .
burning of alcohol .
pound with o ne of oxygen This is the case when ammo nia gas
.
Water is placed
in the ret ort A ,
e d The dissolved
.
which is c o oled by
water in the vessel
D . The c ondensed
water no w p ure
, ,
wate r flows out nea r the t o p The steam thus meets with cooling
.
way very com pletely condensed (princi ple of the counter current ) -
.
c o lle cted .
18 °
of the purest water o bta ina ble to be expressed i n
re ci proca l O hm s ; by th i s i s m ea n t the c ond uc t ivi ty O f a body a c o lum n
water has at 0 the sam e res i stanc e as a c o pper w ire of the sam e c ross
°
e qu ator one tho u sand t im es The sli ghtest tra ces of sal ts or even c on .
1 6 . Wate r at
rdinary tem peratures is an o do rless tasteles s
o ,
co nstants of water its freezing point being called 0 and its boiling
,
-
°
‘
°
5 pe r atmos phere ) This is the reaso n why ice melts unde r
.
The s pecific heat of water is greater than that O f a vas t maj ority
o f other substances I t s latent heat of fusio n is 7 9
. its latent
heat Of vaporizatio n 5 3 6 C al Water is extensively used as a sol .
There are many liquid substances that mix with water in all pro
portions and many also which do not
, ( Se
, e , .
NA TUR A L WA TER .
71Wate r as i
.t o ccurs in nature is by no means chemicall y
, ,
p ur e It may
. contain solid matter in sus p ensio n as well as sub
stances either solid or gaseous in solution The purest natural
, ,
.
in the country ) and gas es from the air as well as traces of amm o ,
nium salts .
some carbo nic acid and air i n solution both of which give i t it s ,
Thi s c ons i sts essent i ally of a ho ll ow c yli nder of poro us por ce l ai n ( c alled
a c andle A thro ugh who s e walls the water i s forced by its own pres
,
the no zzl e .
w ork s on balneology .
s al t
. A large num b er of ele ments V iz about thi rty h av e b ee n
,
.
, ,
found in sea water although the most of them exist there o nly I n
-
ri vers l akes and seas vari es howev er thro u gh m any nu an c es fro m pure
, , ,
may bring about the var i ous b l ue green or brown tints in natural waters }
,
C O M PO SI TIO N O F WA TER .
strong e le c tri c current is then sent thro ugh the wi re a c b so that the fine ,
p artia ll y
. de c o m pose s the
F IG 1 0 —D E COM P OS I T I O N
. . OF WA T ER BY G L O W ING PL A TI NUM .
water vapor i nto hydrogen and o xygen whi c h pass out through the t ube ,
e xpl osive mixt ure 1 3 ) of hydrogen and o xygen as c an be e asil y pro ved ,
by applyi ng a fl am e .
CO M PO SI TI O N OF WA TE R . 23
For this purp ose both the analytic and Synthetic methods can b e
us ed .
( )
a T h e A na l ytic M et h od — When an electric current is p asse.d
through water to which has been added a little sul phuric acid t h e ,
is shown in Fig 1 1 . .
O F W AT E R
o xygen
.
a .
wash b o t tle B t o free it from imp urities and also through the U
-
FI G . 1 2 — SYN
. TH E S I S OF W A T ER A FT ER D U M A S
,
6 I N O R GA N I C C HE M I S TR Y . 20
~
Under the same press u re water always has the same meltin g poin t -
and the same boiling point in whatsoever way it may have been
-
o f c ourse unlimited
,
They are distinguished from com pounds by
.
These pro perties are still evident in the constituents of gun powder .
In a m ixture of sul phur and iron filings one can detect with a micro
s co p e the yellow grains of s ul phur a n d the black p articles of iron ~
.
The iron can be drawn out with a magnet ; the sul phur dissolved
o u t by c arbon disul phide If however a mixture of 7 p arts iron
.
, ,
magnetic and insoluble in carbon disul phide and under the micro
s co p e only a homogeneous scoriaceous mass is seen The constituents .
washing etc
,
.
p ortions. There are for exam ple many sorts of gun powder dis
, , ,
t in g u ish e d from each other by the pro portions in which their con
s t it u e n t s are mixed When 1 p art sul phur and 1 00 parts iron or
.
, ,
o n the other hand 1 part iron and 1 00 parts s ul phur are mixed we
, , ,
o f ben z ene and tur p entine however rises gradually as the more
, ,
not the c ase and where i t i s therefore very diffic ul t to know whether one
is deali ng with a c o m po und or a mix t ure We Shall m eet wi th m any .
PHE N O M E N A AC C O M PA N Y I N G THE F O R MA TI O N OR
D EC O M PO SITI O N O F A C O M PO UN D .
f th e r ea cting s u bs tan c es .
elements unite to form a certain com pound are always the same .
according to human conce ption the smallest particle that can really
b e O bta ined is still ca pable of division into an infinite number o f
o thers However
.
even the ancients,
were of the O i
p nion that there
28 I N O R GA N I C C HE M I S TR Y .
m 21
must be somewhere a l imi t to the divisibil ity and that we must
fin ally arrive at particles incapable of fu r ther div ision the ato m s .
,
.
of the E l eatics (so ca lled fro m the ci ty of E L EA) whose m ost pro mi nent ,
e xperi en c e tea c hes one neverthe less that trans form at i on does o cc ur i n
that whic h e xi sts a fa c t that l e d the m to suppose that everyth i ng
,
N ow DA L T ON
has used th is conce ption of the ancients regarding
the atom to explain the fac t that the combin ing weights are c on
stant The atoms of the various elements he assumes have dif
.
, ,
but also with twice as much not howe v er with any intermediate
, , ,
TH E A TO M I C WEI G H TS O F THE E L EM EN TS . 29
The foll owing statement is therefore now acce pted as a law : When
t wo el em en ts com bin e to form m or e tha n on e com pou nd the differ ent ,
L aw of M u lti pl e Pr o po rt io n s .
of oxygen has a hist ori c reason For a l ong time hydr ogen was .
r e cal cul ation of all the at omi c weights and t his necessity woul d ,
o I N O RG A N I C
_ _ C HE M I S TR Y .
22;
as the
“
of at omic weights criticall y every year Those v al ues are acce pted
international at o mi c weights which appear t o be t h e
.
such as N = 1 4 Br = 80 et c , ,
.
o n ce app arent are t aken fro m the L atin names of the elements ;
e g
. . Sb fro m s tibiu m A u from au ru m C u fro m cu pr u m Hg fro m
, , , ,
rr u m and A g from a rg en tu m
f e ,
.
mine d that in c o pper oxide one atom of co pper is comb ine d with
one atom of oxygen ; co pp e r oxid e is therefore re presente d by
the f o r m u l a C u O which expresses first that we are d ealin g
, , ,
r
p p o e r figure to the right of an d b elow the Symbol Sul p huric .
formul a is therefore H 2 S O 4
, , .
o xy gen an d m ercu ry by
Hg O Hg 0;
K010 3 KC l so ;
Po t a s s . ch l or a t e . Po t a s s . d
ch lo r i e.
Zn + H2 80 4 2H 2 11 8 0 4 .
—
as certaining these will be discussed in d etail later and the atomic
weights of the elements com p osing them also known it is very easy ,
1 000 16
? g Since 1 1 xygen °
. . o at 0 and 7 60 mm .
pressure
21
weighs g .
,
g . o ccupy a volume of
2 How mu ch water can be for m ed fr om the hydr ogen O bta ined
.
su l phu r ic a cid?
yield — g .
65
3 . How ma ny gr am s o f p o ta ss iu m chl orat e ar e n eces s ary to pro
du c e en ou gh oxygen to oxidiz e 5 00 g . copper to c opper oxide
therefore required
g potassium chlorate
.
. Hence
.
500 g c o pp er require
.
W :
2 HC 1 + O E 2 0 + C 12 .
the spring (here the energy of the che mical reaction ) has no t
chan ge d A furt her p oint in the anal ogy is t hat the oil is n ot
.
c onsume d .
for exam ple the m et al uni t es w ith the oxygen whereu p on the
, ,
catalyzer .
kind .
2 6 Physic l
. a P r op er t ies — C hlorine is yellowish
.
—green ( hence its
name which is derived from x71
, greenish yellow ) and has -
g at 0 and 76 0 mm °
ressure At — 3 4 it becomes liqui d
°
.
p . .
“
yellow C hlorine gas dissolves in about o ne half its volume of
.
-
”
water ; The aqueous solutio n bears the name chlorine water
‘
-
.
gas being conducted to the bottom where it remains and drives out ,
27 C h em ica P p i s
. l ro er t e — E ven at ordinary temperatures chlo ,
rine combines with many elements and acts o n many com p ounds .
, ,
m olten sodium etc The pre cio us met als are in general quite
,
.
c hlori d e .
36 IN O R GA N I C C H E M I S TR Y .
l§ § 27
p h o r u,
s which burns in it with a p ale flame to phos p ho ru s
chloride .
chem ica l —
or fit y for the latter is so strong that
f
a ttr a cti no
,
a n it ,
If sul phur etted hydrogen gas HzS is p assed into chlorine wate r
, ,
-
2H2 0 2C 12 = 4 HC l 02 .
c ollects at t h e t op o f t h e r e t or t an d o n investigation wi t h a
, .
FIG 1 4 — SL O W D E COM P OS I T I O N
. .
-
OF W AT ER f
BY CH LO RIN E .
Upon this deco m position of water de pends the bl eachin g and dis infect
in g ac tion of c hl ori ne and t hose s ubstan c es whic h generate c h l or i ne In .
blea c hi ng t h e c o l or i ng m
,
u s u ally of an organi c nat ure— are ox i
atters —
tion O rdi nary at m ospheric o xygen does not produc e these e ffects Lit
. .
chlo r ic aci d
A gC l + H = A g + HCL
N aC l H2 80 4 N aHSO 4 + HCl .
So iu m d p
Sul h u ric
c hl o r i e d . a ci d .
2 N aC l + m o, = N a2s o, 2 HC 1 .
weighs gr .
tures are ea s ily atta inabl e by m eans of liqui d a ir The freshly generated .
gases c ontai n in m ost cases m o i st ure and other im puri t ies The gases .
soli d m ass m el ts first ; the resul ti ng liqui d when vaporiz ed g ives the , ,
p erfe c t l y p u re g as .
The gas fumes strongly in the air forming a cloud with the ,
”
s olution of the gas is called hy dro chlori c acid also m u r ia tic ,
Th e g as it el f i ofte c ll e d
s s n a
“y
h dro h c l or ic aci d g as :
H YD R O G E N C H LO R I DE . 9
p ressure causes only a small increase in the solub ility Such con .
a n d bo il i ng p o i nt res ul ts
-
fro m distilling a m ore d ilu te hydro c hl oric
a ci d
,
eno ugh water bo il ing o ff to ra i se the c on c entrat i on to the above
val ue .
3 0 The
. c h em ica l r
p po er t ie s of hydrogen chl oride are found t o
b e quite d ifferent when it is in a perfectly dry condition e g con
'
,
. .
former case it does not act on metals nor change the colo r of blue
litmus I n the latter case j ust the contrary is true Zinc iron
. .
, ,
ro
p p erties as those that are described here for hydrochloric acid .
, ,
s u ch s u bs titu tion a r e
ca l l ed s alt s
m eta l s tha t ar e form ed by Salts .
can result no t only from the direct action of metals on aci d s but
als o from the interaction of acids and b as e s The term b as es i ’
.
“ ,
a me t al M ost of them have an alka l ine taste and turn red litmus
.
40 IN OR G A N I C C HEM I S TR Y . 30
~
Na H2 O = N aO H H .
N aO H HC l N aC l Hg O .
MO H + HA = MA + H2 0 .
Zn O HQ SO 4 ZD SO 4 HgO .
Zin c p
Su l h u ric Zin c
oxi e d . ac i d . p
su l h at e .
In gener al the bases are built u p from metals the aci d s fro m ,
m etalloids .
A gN 0 3 HC 1 HN O 3 A gC l .
c h l o ri e .
nitric acid from its salt I t is also p ossible to liberate a base fro m
.
A gN O 3 N aO H A gO H N aN O 3 .
Sil v e r d
So iu m
hy d ro x i d e . n it r a t e .
and their absolute purity the gas mixture is prepared by el ectrolysis in the
,
dark and exp osed to the action of li ght i mm ed i ate l y after the tube is filled .
FI G . 15 .
—E L E C T R O LYSI S OF H YDR OC H L O RI C A C ID .
The fact that hydro c hl ori c a c id gas yiel ds a vol um e of hydrogen equal
to hal f i ts o wn v o lum e can al so be shown i n another way When perfe c t ly .
sod i um i n m erc ury the sod ium c o mbines with the c hl ori ne sett i ng
—
,
hydrogen free The vo lum e of the l atter i s then found to be hal f as large
.
2 vols Hg O
. .
e x pl os iv e mixt ure i s i ntrod uc ed i nto the c l osed arm B of the U—t ube o ver
m erc u ry . B i s s urro u nded by a gl ass j a cket thro u gh wh ic h the va por of
,
found that the volum e of s tea m form ed i s two th irds that of the mixture -
.
C O M PO S I TI O N O F H YD R O C H L O R I C A C ID . 43
FI G . 16 .
—D E T ER M INA T I O N O F TH E V O L U M E R E L A TI O N s BE TW EEN ST EAM AND
I Ts COM P O NEN T S .
suppose that the num ber sho ul d be alike for all gases ; b u t this was
soon shown to be I ncorrect I n the synthesis of water 3 vols (2
. .
A V O G ADR O
further supposes tha t the molecules of oxygen h y ,
unio n of hydro gen and chlo rine i s then exp l ained thus : O u t of a
molecule o f e ach two m olec ules of hydro chloric acid are fo rme d
,
H2 012 2 HC l .
1 v ol . 1 v ol . 2 v ols.
2H2 02 2 H2 0 .
2 v ols . 1 v ol . 2 v o ls .
’
3 2 I t follows
. from the above that A V O G A D RO S hy othesis is o f
p
im po rt anc e in two respects : ( 1 ) in furnishing us a mea ns of as c er
C O M PO SI TI O N O F H Y DR O C HL O R I C A C I D .
45
equal volumes of gases under the same conditions contain the same
num ber of m olecu le s the ratio of the weights of these volumes gives
,
§ 2 12 .
’
Asto In order to understand how Av o G A DR o s hypothesis
can fur nish an idea of the number of atoms which the molecules of
elements and of compounds contain let us return to the exam ple ,
the oxygen molecul e Splits into two parts each of which combines ,
46 I N O R G A N I C C HEM I S TR Y . 33
p ounds as,
com p ared with that of hydrogen are then de t ermined , ,
S b stanu ce . Sp G
. .
Q u ant ity of H .
Hydrogen chloride 0 5 .
Hy drogen bromide 0 5 .
Since ,
therefore no com p ound contains less th an h alf a
,
, , , ,
Sub st an c e . Sp G . .
Q u an t ity o f O .
O xygen 16 16
Water . 9 8
Sul phur dioxide 32 16
N itri c oxide .
15 8
C arb on monoxide 14 8
C arb o n dioxide 22 16
D E TER M I N I N G M O L EC UL A R A N D A TO M I C WE I G H TS . 47
co m p ou n ds o f th e el em en t a s ibl th e s m a l l es t a m ou n t
o
f as m an y p os s e;
th e tha t is oun d in in s ta n ce is the weight
of el em en t f any a to m ic .
p o i nt I
. t i s at p resent o n e of the pr i n ci pa l l aws of c he mi stry an d
phys ic s .
Th i s re l at i on has been s ucc essf ully work ed o u t fro m the theory i n the c ase
of gaseo u s substan c es I t has been sho wn that i n all gases at the sa m e t e m
.
3p
produ c t the theory says that = z
or =
§
z
n mu ; p nm u n 2
,
mu
e xpress i on m u is t wice the ki net ic energy of transl at i on of
In t h is z
'
m ole cul es whi c h is the sam e for a ll g ases at the same tem perat ure If
,
.
3
then p is m ade the sam e for t he di fferent gase s or n, t he number of
mo lec ul es per uni t v o lum e must be the sam e for a ll gases
,
.
P V = R T, or R,
p e r at u r e of,
the g as and R is a cons tant which de p ends o n the
quantity and the nature of the gas under cons ideratio n The .
under the same pressure and tem perature I n the a bove equa .
tio n then V is co nstant for all gases and since we have already
, , ,
32
1
. 223 9 3
of g pe r sq cm i e P = 1 0 1 3 2 5 A t 0 the absolute
. . .
,
. . . .
°
PV 1 01 3 2 5 x 2 2 4 1 2
" 8 3 1 55
.
in c g units If the
.
-
. .
p ressure is ex p r essed in millimeters of m er
cury R b ec omes
,
6 23 1 3 .
n o w been
proved that these movements are due to the im p acts
of the molecules ) ; (3 ) the d iffusion velo city of d issolved substances ;
( ) the refraction of light in the atmos phere c ausing the blue c olor
4 ,
O ZO N E .
and the exit tube e are sunk in a vessel of sul phuric acid int o
-
, ,
tem perature ) i t i s part i ally c onver t ed i nto o z one and the m ore so the ,
m ono xi de a c ety lene or other g as) u pon the s urfa c e of liqu id ai r wh ich
, ,
when a rap i d cu rrent of dry air or o x ygen i s all owed to impinge against
a hot N ERN S T gl ower When t h e a i r c onta ins m o i st u re alm ost n o o z one
.
are oxi d ized to phos phoric acid sul phuric acid and arsenic acid , , ,
to ab ove bec ome blue when o z oni z ed air is dire cted agains t
it I odine is de p osited by o z one fro m a solution of p otassiu m
.
iodide :
O rgani c substances are strongly oxidize d by o zone hence n o ,
st uff sol utions like indigo and lit mus are d e c ol ori zed (b y oxida
, ,
st a c e n s uch as c h lorine o
s, b ro mine in t h e pre en c e o f w ate r t h e o xide o f
r s , s
n it o g e n
r h ydro g e n p e roxi de an d t ill oth e rs give clo e ly a alogou s r e ac
,
s ,
s n
o zon e is t h e vio le t c olo pro duc e d w ith an a cet ic aci d so lut ion o f t etramethyl
r
give a straw ye llow color ch lorine an d bromine a dark b lue w h ile h ydrogen
s -
, ,
p e ro xi d e p ro d uc e n o c o lorat i on at a l l s .
globe with two c o cks was first weigh ed when filled with pure
oxyge n and the n when c ontaining oz oniz ed oxygen A fte r .
. .
, .
mg .
,
mg being the we ight o f 1 c c o xygen at normal pressur e
. . .
v X 1 43 + a .
1 2 times as much
1 The molecule of oxygen being O z that of
.
,
HYDR O G E N PE R O XI DE ,
H QOQ .
3 8 Th is com p ound
.
is usually re
p p are d by treating bari u m per
13 3 0 2 H2 80 4 13 3 80 4 H20 2 .
B ar iu m In sol u bl e
d
.
p e ro x i e.
N3 0
“"H
02 i 280 4
= N 3 9 80 4 + H20 2 .
free its atoms have not yet united to form molec ul es so that t he
, ,
give hy drogen peroxide since the zinc and the water generate a
.
water and air I n this case it is the hydrogen released from the
.
p alla d ium that unites with the oxygen M any metals such .as ,
with air an d dilute sul phuric acid for the same reason as in t h e ,
and air A fter a time the water in the bulb gave th e tests fo r
.
r at u r e and melts at
— 2
°
p e
interesting fac t that it decom poses ra pidly in contact with pow d ere d
substances a pparently withou t actin g upon them Finely divided
, .
c ause an ex losion
p .
l Pb SO 4 ; s ul phuretted hydrogen H2 S
'
d elicate test for hydrogen per oxide O ther tests are fo un d in the .
The ferrous s ul phate c arries the active oxyg en of the hydrogen per
'
1
A q ( aq u a) ,
. a fre qu ently u se d r viat ion for
ab b e wa t er of crystalliz ation
I N O R GA N I C C HEM I S TR Y 38
o cc urs water and metallic silver bein g forme d at the same time
, .
lead oxi d e Pb O ,
.
p ower wh i ch i
,
s e v en m ore de l icate than those des c r i bed abo v e A .
Tra c es of the pero xide turn the so l ut ion green The rea c t i on fa il s i n the
0
.
presence of free a c i d .
Uses H
f y g P The co l ors of o l d pai nt i ngs are often
'
o dr o en eroxide .
-
. .
58 IN O R GA N I C C HEM I S TR Y . 40
thr ough however for if the c u p be closed with a perforated sto pper
, ,
seen to rise slowly in the tube till it reaches a defini te height above
t he level outside .
ins erted in the c u p the force which one would have to exert on it
,
tube till the pressur e of the column prevents the entrance of any
more .
p the
, p ressure which n a kg of the gas at the same tem p erature
.
41 The laws of osm oti c pressure find ex peri m ental Veri fi cation in
.
enu n ci at i on of the l aws PFEFF E R i nvest ig ated dil ute s ug ar so lutions and
.
PV = R T, .
C ons t .
really the case in PFE PFE R s m eas ure ments of a queous s ugar so lutions
’
C onst .
60 I N O R G A N I C C HEM I S TR Y .
I§ § 41
g .
51 0 2 87 1 5 1 78
544 3 05 1 78
567 3 09 1 83
o ccu pies a given volume the gas pressure which it exerts is j ust as
,
atm osphere If there is really e quali ty bet w een os m ot ic press ure and gas
.
was fo u nd to be e of an at m osphere or g A 1% , .
PV
—
T
we hav e R = 84 66 4 . The cl ose agreem ent of the two valu es of R
( co mpare p 4 8) pro v es
the e qu ali ty of gaseo u s an d os m ot ic press ure
.
.
and osmotic pressure that the various substances will exert the
same osmotic pressure ; inversely in equal volumes of solution hav ,
in g the same tem perature and osmotic pressure there is the sam e
num ber of mole cules .
are thus able not o nl y to com pare the weights of equal gas volum es
at the same tem perature and pressure and calculate therefrom t h e
molecul a r weight but we cana pply the same principle to soluti o ns
, ,
D E TE R M I N A TI O N O F M O L E C UL A R WEI GH T .
61
since w e know that in solutio ns of the same tem perature and the
s ame osmotic pressure the quantities of the dissolved substances
molecular weights .
were not for the fac t that the calculatio n o nl y requires that it be
known wheth er two solutio ns have the sam e osmotic pressur e not ,
magnitudes which are pro portio nal to the osmotic pressure and ,
p lanation of
.
—
these terms is perha ps necessary When a substance is dissolved
in a liquid the maxi mum tensio n of the va por is less above the solu
tio n than above the p ure solvent at the same tem perature for the ,
p articles of the dissolved body attract the molecules o f the sol v ent ,
hindering the formatio n of vap or o n the one hand and o n the other , ,
freezing point b ; the part a b gives the pressures for the frozen
-
matter ; the part bc for the liquid solvent This latter part is .
always more nearly horiz ontal than the former as has been proved ,
62 I N O R GA N I C C HE M I S TR Y I§ § 4 2~
bo t h e x perirn e nt all y
and theoretically The freezing point of a .
-
liquid is that tem perature at which the solid and liquid states can
exist sid e by si d e indefi nitely This condition requires that t h e .
for instance t h e vapor tension of the solid were greater than that
,
given off fro m the solid co nde ns ing to a liquid and the former grad
FI G . 18 . FI G . 19 .
solid were less than that of the liquid the entire li q uid would , ,
the va por pressure cu rves a b and be of the solid and the liquid r e
—
,
va por pressure is lower than that of the pure solvent so its inter ,
The c onne c tion between these m agnit u des and the os m otic
43 .
tion , c an on l y be in equ ilibr iu m when they are isotonic, i e when they exer t
. .
the s am e os m otic pr es su r e .
D E TE R M I N A TI O N O F M O L E C UL A R WEI GH T . 63
both c yli nders the l eve l of liqui d i s ke pt at the sam e he i ght c o ns t ant ly by
addi ng or re m ovi ng so m e fro m t im e to t ime .
E quili br ium will be estab li shed so soon as the sa m e press ure is e xerte d
by the d isso lved m o le cul es u pon t h e u ni t area of t h e free s urfa c es of the
li qui ds fro m both s i des of the se mi permeab l e part i t i on ; in other words
-
FI G . 20 . FI G 2 1
. .
The p roof of t h i s state ment lies i n the contradic tion to which the
assurn pt io n that i soton ic so lu t ions hav e u ne qu a l va por tens i ons l eads .
are c onne c ted with ea c h other As s umi ng that the vapor tens i on of A
.
they hav e the sam e vapor tens i on B will therefore have t h e sam e .
, ,
the sa m e free zi ng po i nt -
.
4 I s ol on ic
. sol u t ion s wit h the s am e s ol ven t h ave the s ame boilin g—
p oin t .
sam e te m perat ure and vapor tens i on are i sotoni c If these so lut i ons .
hav e the sam e v apor tens i o n (at the i r bo ili ng po i nt) and are isotoni c -
d e pression A we have , ,
AM C onstant .
b e calculated .
6 IN OR G A N I C C H E M I S TR Y .
“
hav e sin c e been found to be r ic h i n potass ium salts bro mi des and other
valu abl e mi nerals so that the waste sal ts of form er days are now the
,
,
“
liquor still contains the most soluble salts among which is mag ,
obtain ed by the use of c hl orine which sets bro m ine free fro m ,
bromides thus : ,
MBr C l = M C I+ Br .
(M Met al ) .
through a tower filled with round stones so that the expos ed sur ,
stant touch with the bromide liquor the most concentrated gas ,
being in contact with liquor which has already yielded the greater
p art of its bromine so that p
, ractically all the bromine is thus
easily obtained The bromine pre pared in th is way always con
.
drie d b y shaking it with concentrated sul phuric acid and then dis
t ill ing again .
Sp g at
. 1 00 parts of water
.
phos phorus ; and powdered arsenic and ant imony take fire when
s prinkled u pon bromine I t is an interesting fact that of the two
.
r eacts vigorously with bromine while the latter does not react with
,
2 atoms .
manufacturing it .
hydr ogen com pou nds For this purpose numerous organic com
.
-o
pounds can be used For exam ple bromine reacts with n aph
.
,
s BI 2 '
S ZHBr .
P h o s p h o ric
aci d .
A s ph O Sph O I l C
'
The most of its salts are soluble in water ; silver bromide however , ,
The com pos ition of hydr obrom ic a cid can be determined i n the
same way as that of hydro chloric acid Since its va por density is .
I O DIN E .
p h ur ic acid .
is a peculiar fact that the alcoholic and the ethereal solutions are
bro w n while the sol utions in carbo n disul phide and chloroform
,
that in the brown solutions the iodine has formed a comp ound
with the solvent whereas in the violet solutions which have very
, ,
n early the same c olor as iodine va por the element exists in the ,
free state .
70 IN O R G A N I C C HE M I S TR Y . 46
liquid .
The v a p o r d e n s i t y o f i o d i n e i s ( a i r = 1 ) at about
A s the te mperat u re ri ses i t grows stead ily s m al l er howe v er
, ,
.
s ubstan c es .
47 . Th e chemica l p p
ro er ties o
f iodin e r esemble very stron gly
those of chlorine and bromine I t s affi nity for other elements is
(
.
in general weaker however than t hat of the two hal ogens men
, ,
p rolonged .
Th e b l u e ’
substance form ed fro m i odine and starch i s not a c om
p ound b
,
u t i s to be regarded as a p rod u ct of the a bsorp tio n of i od i ne by
4 This com poun d can be obta ined by dir ect synthesis from
8 .
its elements and that is really the best method for pre paring it
,
is also used for the laboratory pre paration of the gas but the ,
PI 5 by water
, As was ex pl ain ed in § 4 5 it is possible to use
.
,
a cid .
fro m the hydrogen i odi de for m ed the gas i s all owed to pass over red ,
phos phor u s .
The de c o m pos i t i on of the hal ogen sal t by sul phuric a ci d is even less
ava il ab l e for the pre parat i on of hydr i od ic than for hydrobro m ic acid ,
°
0 and 4 atmos pheres pressure it condenses to a colorless liquid ,
liberation of iodine .
C h ica l
e m Pr op r ti
e e s — Hydrogen iodide has all the charac
.
‘
being given o ff These are ahn os t all soluble with the exceptio n
.
,
hyd riodic acid possesses another pro p erty which is not found in ,
into hydrogen and iodine it can act as a strong reduc ing agent
,
-
that the aqueous Solution of the gas turns brown iodine bein g ,
set free by the oxidiz ing action of the air ; this change is greatly
aided by the influence of light A t a high tem perature hydr ogen
.
DI SSO C I AT I O N .
same stages are passed thr ough in in verse order so that the degre e ,
c oll isions with each other The atoms of a molecule mus t also b e
.
above c ertain limits ; henc e we see a reaso n for par tia l decom msi
In the case of the form ation and deco m position of hydrogen iodide
this can be c on c eived as foll ows : Two HI m o l e c ul es m eet in s u ch a
state of ato mi c m ove m ent that the H ato m s enter the spheres of attrae
t i on of ea c h other and the I ato m s like wise so that H2 and I2 are form ed
, ,
.
.
,
, , ,
A =R +a
in which A B and C re present single molecules O f the su b
,
.
r eaction velocity thus constantly dim inishes This being the case it '
.
,
’= —
is evident that s k a and s h (a x) are not the true expressions
= o
respectively, for the reaction velocity in the first minute and in the
minute fo l lowing the time t They woul d be correc t if the con .
,
d im inishing as ,
it
does in real ity However we can a pproach .
,
Ax
small becomes the exac t expression o f the velocity It is
22
.
dl
7
‘
A +B= C m
o f A and of B are decom p osed at the end of the period t there must ,
— —
be res pectively a x and b x of the two substances present at
, ,
this mo m ent The r eactio n velocity will the n b e propo rti o nal t o
.
Si
g; K '
<
a — x > b —x
( >.
'
5 1
. The manner of ex p ressing the conditio n of equilibri u m is
now plain A ssuming that the reactio n velocity of the o ne system
.
’
is S and tha t of the other S eq u ilibrium must exist when
,
S=S
’
.
x of these are decom posed after a give n period the reactio n velocity ,
de n t l y bimolecular ) is
S C (a x) 2
,
C being a co nstant .
g gr am m ol e
-
in which C ’
is a co ns tant . A ccordingly equilibrium will e xis t
when
C (a
in gases the number of molecules per unit Volume is pro po rtio nal
to the pressur e A ssuming that at a given moment t h e
pressur e of the hydrogen iodide still present is p that of the hydro ,
ff—
lp
k
2
x .
,
. .
I n all such cases the degree of disso ciatio n must be inde pendent
of the volume because an increase or decrease in the latter causes
,
dx
the e qu ation for the vel oc i ty of deco m pos i t i on i s
?
t
a
K (a -
)
x . When ,
52 ] FL UO R HVE .
79
however ,
it is b im o l e c ul ar t he e quat i on be c om es
dx
=K — 2
Wi th the he l p of i nte gra l c alcul us these e quat i ons c an
a ( a x ) .
K=
% ma
where l og i s the nat ura l l ogar i thm and fro m the se c ond
e ,
J .
—
(
'
t a a x )
If now we determi ne x for var i o u s values of t the val ues of K can , be
c alc ul ated ; they mu st be c onstant I f this constancy appears in .
FLUO R IN E .
5 2 This element
. was first isolated from it s com pounds b y
M O I SSAN in 1 886 It o ccurs in nature chiefly in combinatio n with
.
hydro gen potass i um flu ori de i s i ntroduced i nto a c o pper U—t ube ( Fig .
The o pen ends of the U t ube are cl osed w i th sto ppers FF m ade of
-
The c yli ndric al e lectrodes ti of plati num i ri dium pass th rough the -
whic h i s given o ff as a gas at the pos i t ive e l e c trode is first passed thro ugh ,
FI G . 2 2 — PREPARAT
. IO N OF FL U O R I NE BY E L E C R O LYS IS
T .
( A FT E R M O I SS AN )
.
‘
hydroge n it freezes to a white mass that melts at The ,
C hem ica P p ti s
l r o er e — Of
all the elements now known fluorine
p
'
p ounds ,
such as hydrogen p otassium fluoride K F H F which . ,
-
,
at Sp g ( H = 1 ) . at . I t has an extremely
soluble in water .
“
C hem ica l Proper ties The aqueous solution of hydrogen
.
do ubl e m ol e cules i s o ften obser ved for a ci ds (espe ci all y org anic a ci d s) I t .
H 02 4 m o l e cul es
. I?
The mos t irn por t an t pro perty of the gas for practical purposes
is th at it attacks glass ( f c A s a result .it finds extensiv e
u se in e t c h i n g g l a s s
—
G l ass m ay be et c hed in two ways with a so lu tion of the gas or with
the gas i tse lf In the first c ase the et c hi ng i s shiny and transparent ;
.
wh ic h the figures or l etters whic h one des i res et c hed on the gl ass m ay
be dra w n w i th a sty l us Then the ob j e c.t is e i ther d i pped i n dil u t e
H Y DR O FL UO R I C A C ID .
so that when the l atter i s s ubse qu ent ly d isso lved o ff (by t ur pentine or
,
mined in exactly the same way as was done for the analogous
chlorine and bromine com pounds .
,
. .
, ,
c o mb inat ion) c an unite w ith e ach othe r to for m rathe r u n stab l e c ompounds
, .
in t h e g ase o u s s t ate Th e re is al s o a Br F ; c h l or in e a n d flu or i n e h ow e ve r
.
a , ,
do n o t co mb in e w ith e ac h other .
t w o c o mpo u n ds I C l an d I C 1,
I t de pe n d s o n t h e qu an t ity o f ch l or in e prese n t
3 .
combine with water forming acids O xides which show this latter
,
.
pro perty are called a c i d an h ydrides The acids which are thus .
ing one hydrogen atom which can be thus substituted are called
m on o b a s i c .
84 IN O R GA N I C C HE M IS TR Y . 55
'
55 This com
.
p ound can be re
p p ared by p assing c h l o rin e 0 v er
dry mercuric oxide at a low tem perature
p e r a t u r e s I t can
. be condensed by strong cooling to a dark brown -
1; vol oxygen
. This indicates the formula C 12 0 :
.
2Cl gO 2C l z 02 .
2 v o ls . 2 v ol s . 1 v ol .
HY PO C IILO R O US A C I D , E C l O
-
C 12 0 HgO 2 HC l O .
H Y PO C HL O R O US A C I D .
85
Hg o + 2 01 2 + H 20 = Hg01 , + 2 010 H .
So l u l eb .
hy
( p och l orite ) is formed :
2 K O H + C 12 KC l + KC l O + 1 1 2 0 .
2C l O H 2 HC l + 0 2 .
HC l O HC l C 12 Hg O .
The hy pochlorites act j ust like the free acid since the presence ,
of v ery weak a cids e g the carbo nic acid of the air serves
,
. .
,
latter is obt ained by treating lime with chl orine at or d inary tem
86 IN O R GA N I C C HE M IS TR Y .
,
'
other hand when sha ken wi th m er cury gives white m er curi c c hl ori de
, , ,
Cl2 H,o HC 10 ,
as is shown by the facts that the so lu t i on reacts distinct ly a c id toward
litmu s an d that the hypo c hl oro u s a c id c an be separated fro m t h e hydro
c hl or ic a ci d by dis t ill at i on .
57 This gas
. is formed when p otassium chlorat e KC l O 3 is , ,
C h l o ric P e r c h l o ric
aci d . ac i d .
burned sugar .
The following e xperi m ents give one an idea of the vigor with wh ic h i t
c a u ses o xi dat i on ( 1 ) Wh en fine l y powdered s u gar i s mixed caref ull y
.
. .
,
crystalli z ing dish is the n covered with a glass plate The chlorine
— .
Po t . c h l o r it e . Po t . c h l o rat e .
of the bulbs he decom posed the gas the actio n being non ex pl o ,
-
p otash and the residual gas ( oxygen ) was p assed over into a
measuring tube The ca pacity of the bulbs being known it was
-
.
,
2 010 2 C 12 20 2 .
2 v ol s . 1 v ol. 2 v o ls .
This form ula is also confirmed by the v a por density which was ,
C HLO R O US A C I D, E GIO
2 010 , N ap , zN aCio, o, .
C HL O R I C A CI D, HC 10 3 .
however on the addition of a little sul phurous acid the color dis
,
The com position of chl oric acid was ascertained by STA S from
an analysis of silver chlorate A n accurately weighed amount of
.
drive off all the oxygen The loss in weight indicates the amount.
HC l O 4 .
t h e other o xi des of c hl or i ne ; i t ne i ther atta cks pa per nor acts on sul phur
or phosphorus in the co l d .
O XYG EN C O M PO UN D S O F BR O MINE .
6I . Al tho u gh
no c o m pounds w i th o xygen al one are known there are ,
In s o l .
O XYG EN C O M PO UN D S O F IO DINE .
p otash or s oda a c o l orl ess liqui d i s obtai ned wh ic h has other propert i es
, ,
when fresh than i t has l ater When freshl y pre pared i t de c o l oriz es i ndigo
.
.
Late r on these two pro pert i es di sappear It i s therefore to b e s u pposed .
that a hypo i odi te K I O i s first form ed and that this i s c hanged sl owl y
-
2 HI 0 3 HzO I zO 5 ,
3 I2 1 0HN 0 3 6 HI O 3 1 0N O 2 HzO
Nit d Nit d
.
r ic a c i . i
r c o xi e .
ful oxidizing agent setting free chlorine from hydrochl oric acid
-
, ,
2 HI O g 1 0HC l 12 5C 12 6 HzO .
r ather easily .
l emon yell ow c rysta lline powder that brea k s u p into i ts el e ments above
-
on p erchloric acid :
HC l O 4 I 2 H2 0 HI O 4 Q HZO 01 .
N O M E N C L ATUR E .
a general one which is also used for the acids of other elements
, .
The bes t k nown acid usually has the suffix ic e g chloric acid o
- -
,
. .
_ ,
,
. .
, ,
acid etc Thos e which conta in still less oxygen have the suffix
,
.
-
ou s and also the prefix hyp o e g hyp ochlorous acid h yp osul . .
,
ph ur o u s acid and hy o
p p hos phorous acid .
ph u r ic a ci d) and A cidu m s u lp hu r os u m ( s ul ph u ro u s a ci d) .
-
a te
,
e g p otassium
. . c hlorate sul p hate phos p hate T h e salts of ,
-
,
-
.
the ou s ac ids have the ending ite as potassium chlorite sul phite
-
.
-
, ,
-
,
-
,
-
.
, .
there are two oxides the name of the one with the more oxygen ,
,
-
,
. .
,
oxygen than the ou s com poun d is given the prefix hypo and one
-
with more than the ic oxide the prefix per as in the case of acids -
and those s ubse qu ent ly di s c o vered were nam ed a cc ordi ngly a s i n the ,
E LE C T R O LY TI C DI SSO C I A TI O N .
sio n a nd the boiling p oint elevatio n are both greater than they
-
é
9
be expected to Show a de pressio n of — the molecula r
g 5
de pressio n for water 4 3 ) being 1 9 i e A M = I 9 and the m ol e c
,
. .
,
the osmotic pressure i s pro portio nal to the freezing p oint de pre s -
seco nd and still more serious obj ectio n is that an acid or base in
an aqueous solutio n by itself exerts a n osmotic pressur e greate r
than that calculated Here however hydro lytic dissociatio n is
.
, ,
im possible .
The questio n as to the real nature of the divisio n has found its
a nswer in a co nsideratio n of the relation which exists betwee n the
—
bases and salts show the above mentio ne d ab normalities in osmotic
,
p ress u re
. When these substances are dissolved in another liquid
t h an water the resulting solution is a non co nductor but at t h e
,
-
same time its osmoti c pressure again assumes the normal Thes e .
, .
,
have resulted from the mixing of the water and the hydrogen
chloride We were led to surmis e this above
. when it w as
found that this gas solution does not obey H ENR Y S law Sinc e’
.
become electri cally neutral o n c ontact with the latter and esca p e
“
fro m th e liquid Similarly the p ositively charged hydrogen ions
.
a bcd ,
Fig 23 is nearly filled with d ilute sul phuric acid
.
, Th e .
FI G . 23 .
ZIl H2 SO 4 ZUSO 4 H2 .
by the two m ethods The values o pposi te ro were calc ul ated fro m the
.
li ter .
N aN O
0 0 0 0 0 0 0 0 0 0 0 0
66 . I on ic Equ ilibriu m — In
a case of electrolytic disso ciation w e
h ave an equilibrium to deal with namel y that between the u n , ,
disso ciate d molecules o n the one hand and th e l ons on the other .
’
H the hy d rogen ion
’
divide d into two ions each then the equil ibrium is r epresente d b y ,
a — x =K
I t also follows that the degr ee of diss ocia tion depen ds on the con e
above equation
— x) = K n 2 x2 —
) = K 2
n ( a , (a x -
n x
-
.
E L E C TR O L Y TIC D I S SO C I A TI O N . 9
If n is 1, must diminish ,i e
a: . . the ion ization decreases with
in cr ea sin g con cen tra tion I f n is < . 1, must increase i e the
11:
,
. .
ion ization in cr eas es with the dilu tion . When n is in fini tely small ,
we have a =x
,
in other wor d s ,
at infin ite dil u tion the ionization is
com pl ete .
is also formed The acid or base that can ex pel another from its
.
chl oric acid is for exam ple stronger than hydrofluoric acid At
, , .
these common pro perties of acids on the one hand and bases o n
the other in that which all acid solutions have in common namely , ,
t i o n ar e a l m o s t i n v a r i a b l y r e a c t i o n s b e
t w e e n t h e i r i o n s We shall explain this later in many .
ins tances ; the following exam ple may suffice for the present .
take n pla ce we must know t hat in dilute sol uti on mos t salts are
almost wholly s plit u p int o i ons Water itself however i s split .
, ,
H2 O fi H OH
,
el e c tro c he mi stry The res ul ts of the d i fferent m ethods agree well and
.
. .
,
.
-
.
freely side by side ; but not so with H O H for these must unite
’
'
tion of the salt we therefore have only the H and O H ions unitin g
’ '
“‘ ’
of only 3 % of H ions and F ions there is a large excess of these ,
ions in the liquid and almos t all of them must unite with each
’
other whil e the N a and C l ions remain free ; in o ther words
'
, ,
It also becomes manifest that the old notion once very gen ,
e r all y held that the stronger acid ex pels the weaker one from its
,
salts com pl etel y is incorrect When the ex pelled acid or base escapes
.
d eed seem to be com plete ; we shall examine the cas e more tho r
o ughly in 73 .
—
solution of potassium iodide retaining our il lustration contains
—
neither free p o tassium nor free iodine but ion s of pota ss iu m and
ion s of iodin e The atoms however must possess an altogethe r
.
, ,
different energy su pply than the ions whose elec tric charges are ,
this is apparently much different wi th the ions than with the atoms ,
SUL PH UR .
in the United States but large quantities are also found in other
,
FI G . 24 — D
. I ST ILL AT I O N OF SU L PH UR .
hot water under pressure i s forced thro ugh p ipes s u nk thro ugh the
g round to the sul ph u r depos i t thus m e l t i ng the s ul phu r wh ic h i n a
, , ,
The crude sul ph ur th u s obta i ned i s st ill im pure It i s re fined ( Fig 24)
“
. .
s ul phu r The v apor is c ondu cted i nto a l arge brick chamber e qui pped
.
,
with a safety valve for the rel ease of a i r If the dist ill at i on is condu c ted .
so s l owly that the te m perature of the c hamber does not e xc eed the
bo ili ng po i nt of s ul phur the l atter is de posi ted in t h e form of a fi ne
-
layer of liqui d sul phu r on the fl oor It m ay be l e t out thro ugh the .
o pening C and cast i nto s li ghtl y c onic a l wooden m o l ds This is the roll .
py r ite o r i,
r on p y rites F 6 82 which yields sul phur on heating
, ,
3 F6 82 F6 3 S4 28 .
p h i d e s o ccur in nature e g ga l en t,
e .
( lead . sul p hide z n c ,
blende ( s phalerite , zinc sul phide ) s tibn ite ( antimo ny sul phide ) , ,
p h id es ) and ch a l co py ri t e co
( pp er p yrites C o pper and iron sul ,
ll
'
,
A little ab ove its melting p oint -
c ial l y
ab ove it again beco mes mobile the dark color remain ,
it b°
oils roducing an ora ge — c olored va or A t
ing ; at 4 48 p ,
n p .
a n d —
the freezing p oint de pression of fused na phthalene ( melting
oint I the gaseous state the density air = 1 varies from
p n ( )
at to at 860 and then remains c onstant even °
Sz molecules .
atoms ; at 2 000 and atmos phere pressure the disso ciation has
°
known while in the liquid state there are two more The solid
,
.
A mor phous sul phur may be either soft and soluble in carb on
disul phide or p owdery and in s ou b l e in this liquid .
The so lub le ki nd res ults fro m the deco m pos it i on of c erta i n sul phur
co m po unds When hydrogen s ul phi de water i s e x posed to t h e ai r s ul
.
,
liqui d whic h i s found to c ontai n e x trem ely fine part icles of am orphou s
,
1 06 I N O R G A N I C C HE M I S TR Y .
directly Powdered Iro n and sul phur when mixed and heated
.
, ,
fire in the va por of boiling sul phur When mercury and sulphur .
p h i d e s .
THE TR A N SI TI O N PO I N T .
n ary tem p eratu res sul phur is rhombic and rema ins so till the
A t the tem perature named the two mod ifications are equally
stable and can exis t side by side in any pro portions for an indefinit e
p eriod ; above it only the monoclinic below it only the rhombic , ,
The tem perature at which the one system passes into the other
is called the tr an sitio n poi n t also poi n t of i n ve r sio n This transi
, .
tion point possesses great analogy with the melting p oint Just -
.
°
as ice for e xam ple is changed into water above 0 and water into
, ,
the other .
spo n din g to different tem peratures The result is the line marke d .
,
THE TR A N S I TI O N PO I N T . 1 07
latter and take a new dir ection This deflection is very slight in
.
c l u sio n s 43 ass into ice when the two are in contact How
,p .
e ver,
the va por tension of water at a tem perature slightly above
FI G 2 5
. . FI G 2 6 . .
0
°
will b e l ess than that of ic e and we shall have t he ice trans
formed in t o water It is therefore e v i d ent that b oth ab ove
.
d isappe ar .
the tem perature is other than for the same reason as in the
case of the melting po int ; moreover jus t as ice and water un d er
-
rhombic sul phur for exam ple has been placed in the dilato meter
, ,
STAB LE,
” “
M ETA STA B LE ,
AND “
LA BI L E .
but gets further and further fro m the vertical p osition and finally
tumbles over A labile condition is thus really a limiting c ase
.
which c annot actually be realize d ; not even for the c one though ,
its a pe x its equil ibrium has very little stability O n the c ontrary .
1 10 IN O R GA N I C C HE M I S TR Y . 71
gaseous sul phur O r of water and st eam has but one c om p onent
, ,
.
In this case all phases have the same c om p osition There are .
as one of the c om p onents ; but then in case the solid phase was ,
inde pendently in any phase neither are they found in any other ,
s olutions ) .
orate ; since the solut ion was saturated the result will be that a ,
solution and s alt will therefore h ave altered but the co m p osition ,
of each phase will remain the same The tension and hence als o .
,
b eing left .
tem perature there are not sim ply o ne but infinitely many pres
sures under which this system can be in e quilibrium The result .
or in words
, ,
-
The su m o f th e n u m ber o f th e degr e e s offr eedo m a n d
th e n u m ber f
o th e pha s es of a s ys tem ex c eeds th e n u m ber of co m
p o n en ts by two .
Sol id L iq u id R h om b ic
G a s e ou s
FI G . 27 FI G . 28 .
p p ;
o n e degree of freedom or as we say it is u n iv ar i an t To every
, , , .
the rhombic phase passes into the monocli nic phase The or di .
mon to both crystall ized phases and the gaseous phase A t B the .
,
, ,
’
should also be noted that the line B C which se parates the liquid ,
and the solid phases mus t indicate a rise of melting point for an
,
-
’
p ressure The
. lines O C and B C are not p arallel but intersect ,
p h e r e s
. A s the sum of the p hases and degrees of freedom is als o
three with sul phur the p hase rule indicates that all four phases
,
cannot e xist in the p resence of each other at the same time not ,
A t the tri ple p oint neither the tem p erature nor the p ressure
can be changed without altering the kind of equilibrium Here .
only one phase I n the suc ceeding cha pters we shall have
.
“
72 .This gas occurs in nature chiefly in volcanic regions C er .
bodies .
at high tem peratures illustrates the former case while the boiling ,
N one of the above methods is ada pted to the pre par ation of
the gas in the laboratory For this purpose the interaction of a
.
was de vi sed by KI P P whic h c an b e u sed for the ge n é jfat ion (at ordi nary
, .
’
fi gu re (s ee nex t page) .
the u pper gl obe tape rs i nto a l ong t ube whic h fi ts t i ght ly i nto t h e l ower
,
and the d ilu te a ci d i s poured i nto the u pper port i on t h e sto pc o ck rem ai n ,
O n acco unt of t h e free i ron u s u a lly present i n iron sulphide the gas ,
e I N O R GA N I C C HE M I S TR Y . 72
FI G 2 9 —
. . K I PP G ENERA T O R .
Physical Properties —
Hydrogen sul phide is a colorless gas of
disagreeable odor when diluted reminding one of ro tten eggs
, .
7 60 mm pressure
.
water dissolving
The gas is rather soluble in water 1 vol
.
water
C h em ica l Pr op er ties — Hydrogen sul phide is c ombustible and
yields on c ombustion either sul p hur dioxide and water or water
and sul phur ac c ording to the air su pply
,
filled entirely and closed air tight The latter condition is best
-
.
C dS, the brown stannous sul phide SnS the yellow stanni c sulphide
’
, , ,
r est of the sul phi des named are black O ther metals such as .
,
are p reci pitated by amm onium sul phide Still other metals such .
,
solutio n of co pper sul phate into which hydroge n sul phide is being
,
p assed C o pp
. e r sul phate is almos t entirely ioni z ed hydroge n ,
Cu S0 4 + 2 OH +
’
the equilibrium betwee n hydro gen sul phide a nd its ions is dis
t u rb e d ; new HzS molecules are then Spli t u p into ions so tha t ,
there are again S ions prese nt whi ch can unite with co ppe r an d
-
, ,
0 11 80 4 s Cu S 11 2 8 0 4 ,
In so l .
However if these co nditions are not ful filled and as a result the
, ,
‘
,
H Y D R O G EN S UL PHIDE 19
actio n law to the case is very sim ple C o pper sul phide when in .
,
ab= k -
c,
be preci pitated .
of the sul phide will dissolve ; to be sure the H ions of the strong
-
of co pper sul phide must go into solutio n ; but soon the point will
b e reached whe n so many C u and S ions are again in the solutio n -
Fe SO 4 will cause no preci pitate of iron sul phide and iron sul phide
, ,
When hydrogen sul phide is led into a solution of ferrous sul phate
t o the point of saturation the concentration of the S ions is on
,
-
when dilute hydrochloric acid is added to iron sul phide the H ions ,
-
tion
Fe SO 4 (N H4 ) 2S F EES i ( N H4 ) 2 SO 4 ‘
In this case there are no H ions in the solution to act on the iron
-
sul phide .
The reason for the non preci pitation of metals like barium -
etc either by sul phuretted hydrogen or ammo nium sul phide lies
.
,
74 . a
Ifs o l ut i on of sod i um s ul ph i de N a S i s d i gested
, w ith s ul ph
, u r
, ,
the sul phur di sso lv es and the liqui d c ontai ns c o mpounds c all ed pol y
s u l ph i des and havi ng for m u l ae fro m N a S u p to N a s ac c ord ing to the
z 2 ,
alk ali es i t de c o mposes v i ol ently Under ordinary pres sure the liq ui d
.
inc o mbustible A t —
. 5 5 it solidifies with t h e fo r m at ion of crystals
°
.
'
VA L EN C E .
o n the one hand and hydrogen on the o ther are able to form only
p les : H g S Hg O ) These
,
are therefore
. called b i v al e n t .
\H
The valence of one and the same element may be different
according t o the nature of the u nivalent elements with whi ch it
combines Sul phur for instance can o nl y unite with two hydrogen
.
, ,
therefore four and six The prep aration of sul phur compounds .
with m ore than six univalent atoms has not yet been accomplishe d ;
hence it s m axim u m v al e n c e is six .
to each other they dis play more than o ne valence as may be seen ,
fro m the com pounds 1 013 and 1 015 ; in the com pound C l 7 6 0)
the maximum valence of chlorine can even be assumed to be seven .
vale nces are of the same sort ; the halogens and sulphur illustrate
this However these are exce ptions t o this rule
.
,
.
O
xivalent tow ards oxygen at l o w e r tempe ratu / it on ly qu adri
se re s 2 0 ‘
is
on t h e pr e ss ur
l tt e x e rt a g t i nflu e n ce o n t h e di o ci tion
e, fo r t h e a er s re a ss a .
as s or e a e so o o s e a, o ro e o or
ch mi try t h t t h t m f a m le cul e m y t
e s ,
a e a o ume y co c ivab l e
s o o a no ass an n e
Vale n c e I on s —I n
the solutio n of an electrolyte the sum s of
of .
all the p ositive and all the negative a m ounts of electricity must
77 . O f those
o nly the two elements three are known
c o n t a1 n 1 n g ,
viz S 2 0 3 SO Z and SO 3
.
, ,
E s pecial im p ortance attaches itself
, .
,
studied .
l
Su ph ur Se s q ui oxi de ,
820 3 .
Water de c o m poses it with the form at i on of sul phur sul phuro u s a ci d and ,
po l yth i on ic ac i ds .
when sul phur burns in the air or in oxygen ; the well known odo r -
2 H2 8 0 4 CH 011 80 J "80 2 H2 0
4 r 2 .
Fo r this pur pose co ncentrated sul phu ric acid is heated with c op
e r tur ni ngs no act io n taking p lace at ordinary tem p eratures
p ,
.
The pro cess can be ex plained by supposing that at the high tem
"
1 26 IN O R G A N I C C HEM I ST R Y .
Q
vols .
SO z at,
20
°
vo l s SO z . . B oiling the solutio n ex pels all t h e
gas
C h em ica l Prop er ties dioxide i s an acid a nh ydride ;
— Sul phu r
I t s aqueous solutio n has an acid reactio n and behaves in general
and iodine :
Pb O z S0 2 Pb SO 4 .
.
,
for exam ple loses color in it The gas probably reacts with
,
.
80 2 2 H2 0 11 2 80 4 H2 .
—
of s ul phur d i o xi de i odi ne be i ng s e t free
I f the react i on i s c arr i ed o u t i n dilu te so lu t i on a pec uli ar pheno m enon
,
is observed ; the b lu e c o l or of star c h i odi de does not a ppear d ire c tly when
t h e so l ut i ons of s ul ph u r d i o xi de and i odic a ci d are mixed b u t i s w i th ,
reactions co m e into pl ay
ph id e and sul phur dioxide have res p ectively an oxidi z ing and a
reducin g effec t on each other which follows mainl y the equation :
,
2 11 2 8 80 2 2 H2 0 + 3 8 .
heated by the s par ks are imm ed i ate ly c oo led aga i n by s urro unding
obj e c ts A s a res ult t h e produc ts form ed do not have t im e to rea c t i n
.
rapi dly that the t ube m ai ntai ns a l ow te m perat ure When DEVI LL E .
introduced sul phur d i oxide i nto the s pa c e between the two t ubes i t was ,
seen after so m e t im e that the i nner t ube whic h was m ade of s ilver plated
,
-
barium c hl or i de) .
tain two atoms of oxygen The s pecific gravity of the gas has
.
79 This
. c om p ound is found in a small amount in th e fume s
sul phur dio xide u ni te t o form the trio xide in the p resence of
p latinized asbestos O n the other hand
. the trioxide breaks up
,
2 80 2
02 3 280 3 .
8 0 Physica l Pr op erties
.
— Perfectly dry sul p hur trioxide melts at
1 7 7 and boils at I t looks much like ice but usually a ppears
°
.
s ubl ime on heat ing This modification is the stable one for the
.
,
C h em ica l P p
r o er ties — Sul phur trioxi d e u nites ver y easily with
water to form sul phuric acid
80 3 HgO 11 2 80 4 .
p l e glows
,
in contact with it When its va p or is p asse d . through
a r ed hot tube it is decom posed into the dioxide and oxygen
-
, .
p roducts S 0 2 ,
and 0 2 are formed in the
,
volume ratio 2 : 1 N o w .
2 80 3 2 80 2 02 .
2 v ol s . 2 v ols . 1 v ol .
O X Y G EN A C I D S O F S UL PH UR . 13 1
O xyg e n A ci ds of Su l ph u r .
2 . Hypos ul ph u ro u s a ci d H2S2 0 4 .
3 . Sul ph uro u s a ci d .
4 . Sul ph u r ic a ci d .
H2SO 4 .
5 . Pers ul ph u r ic a ci d . HzSzO S .
6 . Di thion ic a ci d HZSZO G °
7 . Tri th i onic a ci d H2 S3 O B .
9 . Pentath i oni c a ci d Hs O B .
sul phu r i c aci d has really been isolated ; all the others are kn own
gen atoms which each o f these acids possesses are both replaceable
by metals ; they are therefore diba sic acids With such acids it .
but in that of the acid salts MHA the ions are chiefly M and HA ’ '
.
How far the anion HA is Split u p does not de pend m erely o n the
’
.
o f t h e same concentration .
e ven then very unstable decom p osing com pletely in a short time
,
.
The salts are however s table and can be prepared in the following
, ,
13 2 IN O R GA N I C C H E M I S TR Y .
M 82
SO 3 S S2 0 3
2 08 82 3 02 2 03 82 0 3 .
C al c iu m di
su l p hi d e .
ph ide
4 N ag S 68 0 2 4N a2 S2 0 3 S2 .
“
and even yet often called sodium hyp osul phite or abbreviated
hyp o ”
I t is very soluble in water ; the solution when used in
.
,
,
, ,
excess has the pro perty of dissolving readily the halogen com
,
, .
chlo rine for example Practical use is also made of this latter
,
.
ro
p p erty by em p loying sodium thiosul p hate as an a n tichl or in
bleaching i e to remove the last traces of chlorine which cling t o
,
. .
the bleached material very obstinately and have an inj urious effec t .
A n io n o f s u l hur
o u s ac 1
supposed that the thi os ul phu ric a ci d re m a i ned ent ire ly unc hanged u nt il
’
however the solution obeys this law pretty well A fact in con
,
.
firm at io n of this is that all the sul phur dioxide can be ex pelled fro m
the solution by boi l ing it the combination being then wholly ,
all s oluble in water while of the neutral salts only those of the,
alkalies are soluble The acid sodium sul phite N aHSO 3 (sodium
.
,
SULPHUR I C A C I D, H ,So , .
J
85 Sul phuric
ac id is the most im p ortant a c id of sul p hur It .
can be formed directly from sul phur and oxygen and this yields ,
on oxygen comp ounds may also give sul phuri c acid ; thus it is
formed when concentrated nitric acid HN O 3 is boiled with sul , ,
hur and again otassium sul hate is fo r med by hea ting sul hur
p ; p p , p
with saltpetre ( K N O g) .
air of lower oxides of nitrogen formed from the nitric acid in the
p revious reactio n These .are p artly reconverted to nitric acid
a nd partly changed to certain stages of oxidatio n of nitrogen
which oxidize sul phur d ioxide anew to sul ph uric acid By this .
last pro cess the lower nitroge n oxides are again formed but are ,
and these are no lo nger able under the conditio ns of the indus
,
The chemical pro cesses which lie at the basis of the manu
facture of sul p huric acid will be taken u p a little later
From a techni cal stand point the lea d cham b e r pro cess fall s -
.
,
p yrite ; that re
p p ared from the latter almost always co ntains
arsenic The roasting of the pyrite is carried o n in furnaces the
.
,
e ver the sul phur dioxide leaves the furnace m ixed with a good
,
deal of air The furnace gases pass through a canal in which the
.
( )
2 The oxidation of the sul phurous acid is car r ied out in a
str ucture c onsist ing chiefly of thre e parts the G lover tower , ,
flows down over the stone in the tower fro m a horiz ontally re v ol v
ing tube From the G lover tower the gases enter the l ead c h am
.
13 6 I N O RGA N I C C H E M I S TR Y .
86 ;
ber s . These are three or four in number and have a t otal c ap acity
of 4 000 5000 cubic meters Their form is that of a p arallelo piped
—
.
,
lea d c hambers are c onnected with each other with the G love r ,
in the lead chambers the residual gas p rincip ally nitrogen p asse s
, , ,
serves to c ollect the nitrous vap ors that are still present in t h e
gas as it leaves the lea d chambers These va p ors dissolve in t h e .
sul p huric acid forming the nitroso sul phuric acid which is use d
,
reduc ed .
tower .
The gases that c ome from the pyrite furnace c onsist of a mix
ture of sul phur dioxide and air a larger pro p ortion of the latte r ,
fro m the G ay L ussac tower dilute d with the acid ( cha m ber a cid)
-
9 6 9 8% H2 SO 4
— It is prepared from the chamber acid by ev dp
.
a platinum vessel .
13 8 IN O R G A N I C C H E M I S TR Y .
86
2 80 2
2
29 1 19 2 K P3 2
~
or 2
”p1 p = K 2
2 p3 ,
C al ,
S ULPH UR I C A C ID . 13 9
the aid of a fresh p ortion of the gas mixture as the next p aragraph ,
sets forth .
first p ass around the outside of the tubes and are thus warmed to
FI G 3 1 — C O N T A
. C T PR O C E SS
-
A PPAR A T US .
the desired tem p erature at the heat exp ense of the gas system
within When the pro p er tem perature is reached the gases are
.
allowed to enter the tubes where sul p hur trioxide is formed with
,
rate of flow of the gas current the tem p erature can be regul ated
very satisfactorily When the O peration is started the app aratus
.
sulp hur trioxide fumes invariably esc aped when this substance was
introduced into water or dilute sul p huric a cid O nly when sul .
which is only slowly absorbed by sul p huric acid ; sec ond that at ,
8 7 Physi l Pr ope ti s
. ca r e — The pure com p ound hy droge n sul ,
p hate ,
is an oily liquid at ordinary tem p eratures solidifying at a ,
low tem p erature and melting again at Its Spe cific gravity
in the liquid state is
C hemica l Pr oper ties — The co nce ntrated aci d o btained by ( 1 1 8
.
the distilled produc t must be mixed with the theoreti cal amount
o f s ul phur trioxide Whe n pure sul phuric acid 1 s heated it begins
.
,
into water and the anhydride ; this disso ciatio n is com plete at
for the va po r density at that t em perature is found to be
while that of S0 3 + HzO is theoretically
Whe n sul phuric acid is mixed with water a stro ng evolutio n ,
mixing them in the reverse way by pouring the water into the ,
sulphur ic aci d the inte nse heat tha t is produced may cause the
,
If thes e pyrosul phates are heate d still higher they give off , sul p ur h
t rioxide and form neutral salts :
N a2 S2 0 7 N a2 so4 80 3 .
all other mineral aci d s from thei r salts In the manufacture of soda
.
The determ ina tion of the con cen tra tion of su l ph u ric acid is an .
areometer T here are tables so pre pared that the pro p ortion of
.
C HL O R I DES O F SULPHUR I C AC I D .
the addi tion of water a vio l ent rea c t i on o cc u rs produ cing hydro c hloric ,
a ci d and s ul phur ic a ci d :
so,HC I + H, o H,s o, + HC L
so,ol , + HCI .
H,so, + 2 HCI .
The se de c o m pos i t i ons of s ul phu ryl chl ori de can be represented in the
fo ll owing way :
1
0 1 H | O H
802 SO 2 + 2 H0]
[C l H IO H \ 0H
Pe r su l ph u r ic A c id, m , os .
. .
HSO ’
, the l atter are d i s c harged at the anode an d c a n then uni te to
form H S O wh ic h form s wi th the K i ons present the diffic ul t ly solubl e
z z s,
p otass i um sa l t K S O Th i
z s se
z p arates out
s. as a wh i te crysta lli ne m ass .
1 44 I N O R G A N I C C HE M I S TR Y .
91
However, the c om b inat i on of two HSO groups only ta kes pl ace when 4
into H 0 an d 0
2 Suc h a h i gh c oncentrat i on at the anode i s reached
.
very hi gh there .
2 K 2S20 8 2 K28 20 7 02 .
K -
py r os u l ph at e .
8 0 3 + H20 2 HzSO s,
2 2 + HC I .
\ C l + H20 2 \ O OH '
p os i t i on .
C A R o s a ci d reacts w i th another m o l e c ul e of c hl o rs ul ph on ic a ci d
’
form i ng persul phuri c a cid wh i ch can be obta ined in th is way pure and
,
p
os i t i on ) A
.
so l u t i on o f C A R o s a ci d in sul phu ric a ci d can be prepared
’
I t has v ery strong oxi dizing p owers I t sets i od ine free fro m .
p
otass i u m i od i de ox,
i d iz es s u lphu r d i oxide to tri oxide and ferro us t o ,
I N O R G A N I C C HE M IS TR Y .
93 . On
adding sodium thiosul phate to an iodine solution t h e ,
2 N a2S2 0 3 2T N a2 S4 0 6 2 N aI ;
or, w riting o nly the ions that take p art in the reacti on _
” = ” ’
2 S2 0 3 + 2 I S4 O e + 2 I .
The d isa ppearance of the color is thus due t o the fact that t h e
molecules of iodine are transformed into I ons by taking u p t w o .
for deter m ining the amount of free iodine in a solution This is done .
iodine molecules have now enti rely disa ppeared Since according .
“
1 27 i e a certain amount bleaches exactly this much iodin e
N o rm al sol u ti on
. .
of analytical chemistry .
( Fig
. a glass tube that is divided into 3
1
7, c c and closed at . .
the lower end with a glass sto p cock or with a rubb er tube an d
—
p inch clam
-
FI G . 32 — PI PE T TE
. . FI G 3 3 — B URE T T E S
. . AND SUPP O R T .
necessary before the color com pletely disa ppeared R equired the .
1
13
equivalent of iodine ( = l2 7 c c therefore decolori
. z es . .
{
ix - E g iodine
. . This amoun t is contained in 50 of
1 000
14 8 IN O R G A N I C C HEM I S TR Y .
m
the io dine solution in questio n Hence 1 liter of the latter con.
tains g iodin e . .
sinc e they set free the equivalent amount of iodine from potassium
iodide solution .
SEL EN IUM .
94 . l e nSe
i u m was discovered by B ER ZE L I U S in 1 81 7 I t .
took its name from d e liriu m ( the moon ) because it p ossesses great ,
“
,
The pro c ess i s as foll ows : Th e sel enium de pos i t is heated with nitric
a ci d wh ic h o xi d iz es t h e se l en ium to se l en ic a ci d H Se O
,
Th e so lu t i on , z 4.
thu s obtai ned i s first bo iled wi th hydro c hl oric a ci d whereby sel eni o u s ,
in a m orpho u s r e d fla kes .
Selenium dis plays analogy with sul phur in many res pects ; fo r
instance in o c cu rr in g in various allotro pic co nditio ns A ccording
,
.
selenium fusing at 1 7 0
,
The n there is a metallic form fusing
°
ph u r ic acid The barium. sal t of the acid like that of sul p huric ,
T e ll u riu m .
s yl v a n ite or gr a phic te l l u r iu m )
,
I t is fo und c hi e fl y i n Transylv an i a and
.
white of a m etalli c l ustre and a c ond uc tor of heat and electricity The
, .
increas ing te m perat ure and does not re m a i n c onstant t ill abo u t
it then c orres ponds to a Te2 m o le cule .
Hydr o g e n t e llu ri de H2Te res ul ts fro m the a c tion of hydro c hl ori c acid
, ,
Tell u ric aci d HZTe O 4 is pre pared by f u sing the m etal or the d i oxide
, ,
with soda and sal tpetre and se parat i ng the a ci d fro m the te llu rate form ed .
re
p p ared i n th i s way i s a wh i te p owder d iffi c u l t l y so lu b l e in c o l d water ,
.
SUMM A R Y O F THE O XY G EN G R O UP .
96
The elements oxygen sul phur selenium and tellurium
.
, , ,
like the halogens form a natural group particularly in two res pects
, ,
their com pounds corres pond to a general typ e and their physical
an d chemical pro perties vary gradually with increasin g atomic
weight Their hydrogen com pounds have the formula R Hz t heir
.
,
oxygen com pound s and their acids the formulae R 0 2 and H2R 0 3 ,
At o mic w e ight
Spe m fi c gra vity . 1 95 2 0 7
.
-
M e lt in g p o i nt -
.
Boi n li g po in t
-
.
l
C o or
The insta bility of the hydrogen com pou nds increases from oxygen
to tel lurium ; the str ength of the oxygen acids diminishes rapidly ,
sulphu ric acid b elong ing to the strongest and telluric acid to t h e ,
al l o t r O pic mo dificatio ns .
1 52 IN O R G A N I C C HE M I S T R Y . 97
TH ER M O C H EMI STR Y .
97 . state d ab ove
I t w as 2 0) that a chemical comb ination o r
d ecomposition is accomp anied by an evolution or abso rption of
heat in other words by a heat change or c al o r i c e ff ec t In many
, ,
.
cases this caloric effect has been carefully measure d The work .
The calo ric effec t is always given for molecular amounts of the
r eacting substances , since in this way only is it possible to compare
substances from a chemical stand point Hence when the h e at of .
,
2H O Hg O C al .
far as this is not self evident because the latent heat of fusio n
-
amoun t ,
2H O H2 0 1iq uid C a1 .
,
1 54 IN O R G A N I C C HE M I S T R Y .
( )
1 2 N aO H HQ SO 4 aq N a2 8 0 4 a q 2 H2 0
N aO Ha q Hg SO 4 a q N aHSO 4 a q Hg O
( )
2
N Q O Haq
I N aHSO 4 a q N a2 8 0 4 a q Hg O
C al .
N H3 g a s HC l g as N H4 C l s o l id
N H4 C l s o l id aq N H4 C l aq
C al .
in t he secon d case
N H3 aq N Hg aq
Hcl aq HC l aq
N Hgaq HC l q a N H4 C l aq
C al .
The final effec t s in the two cases are found to be alike withi n t h e
l imit s of ex perimental error .
below .
, , , ,
consider the two ways b y which it can form water and sul p hur
dioxide : ( 1 ) hyd rogen an d s ul p hur are burned dire ctly t o water
and sul phur dioxide ; (2) (a) hydrogen and sul p hur combine and
(b) the resulting hydrogen sul phide is burned to wate r and sul p hu r
d io xi d e Sin ce we started with the same system and in t h e en d
.
reache d the same result in each case the caloric e ffect must be t h e ,
H —
0 H20 ) S 2 0 — SO Z)
( 2 (
H — H
( 2 + S 2 S) (H2S + 3 0 — SO Z -
H20 ) .
68 0 + 50 +
x= ( S + 2 H -
HzS)
2 (2 H —
s H2 S) + 3 (2 o oz ) 2 soz + 2 n zo C l
p a .
2 (2 H H2 ) ( 0
2 0 2) 2 H2 0 q C al.
;
(2 S S2 ) 0 2) 2 S0 2 + r C al
( 0
2 etc indicating the heat of decom positio n of molecules
.
,
o f the elements .
from which it follo ws that the heats of formatio n of the sul phu r
an d hydrogen molecules a r e included in the hea t of formati o n
found .
C HEM I C A L A FF I N I T Y .
( were in“
o n e another which were in a certain agreement with each other
for exam ple defined it as the force which holds the p a rts of a
,
amount of work will be the greater the greater the counter force ,
between this counter force and the driving force of the system .
For measuring affi nity we can thus make use of the sim ple
mechanical n otions which serve for the measurement of forces
in general as for instance in an ordinary weighing We o ppose
, , ,
.
The total energy c ontent of a body c ons i sts accord ing to HEL M
-
H O L T Z of free an d bound en e
,
rgy Th e free energy al one i s c apab l e .
i nto work but only seem s to in c rease the m o l e cular m o vem ents of the
,
thermi c .
TH E R M O C HE M I S TR Y . 1 59
t h e reaction in question .
’
al e n t amount of each com p o und requires according to FA R A DA Y s
,
force must be pro p ortional to the affin ity ; in other wo rds that ,
THE DI S P L A C EMEN T OF EQ U I L I B R I UM .
( g
e . 2 H 2 +
.
, the position of this equilibrium is d e pen d
ent on various circumstance s The relati onshi p is ex presse d b y .
the rul e of LE C HA T E L I E R Z
Wh en an y s ys tem is in physical or c h e m ica l equ ilibriu m a ,
c ha n g e in on e o
f its equ il ibr iu m fa c tor s p r o du c es a c h a n ge in the
s ys t em , fiec t is opp osite to tha t of th e form er chan ge
w hos e e .
the rul e .
p ressure exerted on it .
(2) M onoclinic sul phur when com pressed near the transition ,
over into rhomb ic sul phur since this pro cess involves a lessening ,
p revious case .
( )
5 I n p artially disso ciated N 2 0 4 an increase of p ressure drives
back the disso ciation while diminution of pressure increases the,
’
c ase of L E C HA T E L I E R s rule but was derived from thermodynamics ,
1 62 IN O RG AN IC C HE M I S TR Y . 1 04 1
least only very slowly when they are cooled to a low tem pera
,
ture I n general the rea ction velo city lessens as the t em p erature
.
,
attribute the non o ccu rrence of reaction s which are therm odyna m
-
ic all y p ossible .
I t has been found that the variation of the reaction velo city
‘
with the tem perature may in general be ex pressed thus : when the
tem perature increase s arithmetically the velo city in creases geo ,
N I TR O G E N .
when burned in the air absorbs the oxygen to form phos phorus ,
N I TR O G E N . 1 63
n itrogen lef t .
the ai r i s first passed thr o ugh amm oni a water t h e pro cess can be c arri ed ,
m o niu m carbo nate M ois t phos phorus combines with oxygen even
.
in co ntact with pieces of phos phorus for some minutes loses its
o xygen .A n alkaline solutio n of pyrogallol also has the ability to
ab sorb oxygen at ordinary tem p erat u r es These r eactio ns are .
N H4 N 0 2 N2 2 H2 0 .
di chr o m ate KzC r20 7 i n 3 parts of wate r The N H4C1 and K N O 2 react to
, ,
.
K2 0T20 7 2N H4 Cl N2 l ““ C I '
20 3 2 KC l 4H2 0 .
At — 2 1 4 it becomes solid
°
I t is o nly slightly soluble in wate r ,
.
e leme nts combine directly with nitroge n at red heat form ing ,
bath prevents the decomp osition of the nitri d es forme d in the arc .
the fact that nitrogen is not able to su pport comb ustion serve fo r
the identification of nitrogen gas .
of all b urning and o xi dat i on I t now re qui red only a ste p to rea c h the
.
1 08 . C on s titu en ts
f th e B esides oxygen an d
o A t m os pher e —
etc .
with th e globe V all air having b een removed from both The en d
, , .
w eighing the globe the amount of nit r ogen which it contain s can
b e determined and by weighing the tube before and after we can
N O RDEN S KI O L D ( St ck h lm
SC H EE L E
o
“
it is e vi d t th t xyg n w s k w n to
o
r th t PR I E ST L E Y ; h e c all d it F
soon e an o l ft
,
H w e v e r th is e
en a
e ue r u
o e
.
”
a
o
no
d i c v y did n t e m t l d h im n y n re r th n PR I E S T L E Y to a c o rre c t
s o er o s e o ea a ea a
— A NA LYS IS AIR .
with 1 vol oxygen one third of the volume tha t disa ppeared must
.
,
-
the c om pos ition of the a ir is n ear l y con sta n t I n all parts of the .
reached it consists of
,
M oreover the com po sition does not a ppear to change with time ;
,
and nitrogen are constantly be ing removed from the air and again
r eturned to it and it does not necessarily follow indeed it is rather ,
; the nitro
gen ph os phorus sul phur and other elements return t o t h e
, ,
”
mineral state as nitrates sul phates etc A long with this
, , ,
.
res piration of animals and plants and the burning of fuels carb o n ,
c alcul ated that every year the plants assimil ate milli on milli on
kil ogram s C 0 whic h i s alm ost i s of the total carbon d i o xi de i n t h e
2,
startling resul t that onl y about 2 % of the exi sti ng pl ant m ateri a l i s
engaged in the c yc l e w i th the anim al li fe Al l the rest of the carbon.
nitrogen from the air directly There are also bacteria which.
,
of the o xygen and the nitrog e n of the air in l iquids is the same
as that c alculated fro m the solubilities of the p ure gases oxyge n
an d nitrogen after taking int o accou n t their p artial p ressure s
,
.
for exam ple is led into a flask co ntaining liquid air it falls in
, ,
the solid form like snow fl ak e s I n s pite of its low tem perature
-
.
M g + C aO = M g O + C a,
When cal cium carb ide (better mixed with 1 0% calcium chl oride )
,
2 GaC 2 02 2 C a0 4 0 ; C aC 2 N2 C aC N2 C .
ing that no one has yet succeeded in p re p aring a com p ound of argon .
melting p oint are constant and the va por p ressure of argon like
-
,
:
172 IN O R GA N I C C HE M I S TR Y E
§§ 110
howe ver in obta in ing i t in s m all a m ounts on heat ing the rare mi neral
,
for instan c e those of B ath ; and at l ast i t was a lso d i s c o v ered in the a i r
, .
p art of liqui d a i r D E W AR p ro
. v ed that he li u m and neon c an be i so l ated
d ire c tly fro m the a i r by bringing the a i r i n c onta c t w i th i gn i ted c harc oa l
at The c harc oal has the cu ri o u s property of c ondens i ng i n i ts
p ores a ll the other gases of the a i r and a gaseo u s res i,
d u e i s here obta i ned
wh ic h shows c l early the spe c tra l lines of He and N e .
res i d u e after a l arge quant i ty of liqui d a i r had been all owed to e vaporate
,
C om po u n ds of N it r o gen an d Hy dr o gen .
hydraz in e (N Hs N sH an d N 2 H4 N 3 H)-
O f these five c o m p oun d s
~
.
,
AM M O N I A .
milk of lim e and the e xpell ed amm oni a i s l e d i nto con c entrated s ulph uric
a ci d In thi s way crystalliz ed amm onium sulphate i s obtained I t i s
. .
2N O 5H2 2 N H3 2H2 0 .
M g3 N 2 3 H2 0 2 N H3 3 M g0 .
A M M O N IA .
1 75
see O R G . C HE M .
,
2 66 .
P hysica l Pr op er ti es — A mmonia
at ordinary temperatures is
a gas with a characteristic o d or that excites one to tears Its , .
( O = 1 6) or 1 ) 1 1 N H3 at 0 an d
s pecific gravity is (air .
°
C hem ical Proper ties The characteristic pro perty of this com
.
-
N H3 + HC 1 N H4 C l . N H3 HN 0 3 N H4 N 0 3 .
Am m o n iu m Am m o n iu m
c h l o ri d e . m t rate .
2 N H3 H2 80 4 ( N H4 ) 2 80 4 .
Am m o n iu m
sul ph at e .
m
,
g a m I f
.
sodium amalgam is allowed to react with am onium
io di de dissolved in liquid amm onia a t a hard metallic mass
1 76 I N O R G A N I C C H E M I S TR Y . 1 12
2 N H4 2 N H3 H2 .
and hence also the ions N H4 and O H in analogy with other soluble
b ases e g p otassium hydroxide K O H A S a matter of f act
,
. .
,
.
,
known fact that ammo nia can be entirely ex pelled fro m its
a queous solutio n b y b oiling .
oxygen conveyed by soil bacte ria may also cause the oxidation of .
n it ri de Mg gN z
,
When ammo nia is conducted over hot potassium
.
being doubled :
2 N H3 N2 3 11 2 .
2 v ol s . 1 v ol . 3 v ols.
N HZ C I
2 ,
i t i s a liquid at
ord inary te m perat ures an d free z es be l ow
L O B R Y D E B RU Y N showed that t h e m o l e cul e of water c an be re m o v ed
b y tre at m ent w i th barium o xi de and that the fr ee hydr a zin e c an be
obtained in t h e pu re state by d i st ill at i on u nder red uc ed press ure Thi s
'
s ubstan c e i s liqui d at ord inary tem p erat u res c ongeal s at and boil s ,
:
e ra t u r e s
p .
Hydra zine ,lik e amm oni a u ni tes w i th a ci ds d ire c tly to form sal ts; i t
,
zine i s strongly bas ic I t s sal ts are eas ily so lubl e in wat er e xc ept ing
.
,
HYDR A Z O I C A C I D,
5
1 1 Th i
. s interest i ng c o m p o u nd lik e the p re c ed i ng one w a s first
, ,
hydra z ine hydrate w i th a m yl n i tri te and sodi um al coho l ate whi c h giv es ,
C d and M g
,
I t is c hara c ter i st ic of the m eta l h ydr az oat e s ( or a zi des )
.
”
that they c rystalliz e anhydr o us and y ie l d the pure m eta l when heated .
C o m po u n ds of N it r o g e n with th e H al o g e n s .
un der the mouth of the flask These dro ps contain some hydrogen
.
N C 13 4 N H3 3 N H4 C 1 + N 2 .
N 3 Cl N C 13 C al .
N C l + 2 N aO H
. N aN 3 + N a O C l + HzO .
I o di I
N itrogen i de —
a solution of iodine in p otassium
71 1 .
ex plosive .
.
,
solutio n it is stable .
N HzI HC l N H3 1 01.
Hydr o xyl am i n e , N H2 O H .
Th e free hydro xyl amine i s best prepared by heat ing the phosphate .
p
ress u re at W hen heated in the a i r i t e xpl odes wi th a ye ll ow
fl am e
182 I N O R GA N I C C HE M I S TR Y .
l§ § 1 19
°
N 2 O at 0 and 7 60 mm p ressure weighs . g It is rathe r .
s oluble .
the fact that it gives no red fu mes when mixed with nit ric oxide
1 2 0) and always leaves residu al gas ( nitrogen ) after a combustion .
’
mercury It is easy to ex plain B E R T H E L o r s observation When
.
'
.
evolving still more heat and so o n The wh ole mass will thus
,
.
C omposition — Un d e r
the protracted action o f in duction s parks
the gas s plits u p into a mixture of nitrogen and oxygen the volume ,
p otassium and sodium are burne d in the gas potassium and so dium ,
o xides res p ectively are formed together with nitrogen ; the gas ,
w as foun d to be
NI TR I C O XI DE, N O .
co pper to act on nitric acid or else by cove ring co pper (in the form
o f thin sheets ) with a saturated solution of salt petre and ad d in g
3 Cu 8HN0 3 3 C u (N 0 3 ) 2 4 H2 0 2N o .
I n order t o p re p are nit ric oxide by the reduction of nit ric acid
or a ni trate a boil ing hot solution of ferrous chl o ride EeC l g in
-
, ,
hydrochloric acid is foun d very satisfac t ory ; the ferrous chlo ride
is conve rted into the fe rric chlo ride FC CI3 b y t h e reac ti on : , ,
Perfe c t ly pure
ni tric oxi de i s obtai ned by treat ing a mix ture of yell ow
pruss i ate of p otash and potass i um n i tr i te w i th a c et ic ac i d :
2K 2K N O 2, + 4 0,H 0 2 + 4 K C, H3 0 , + 2H,o + 2N O
Ye ow p rus Po t n i
.
-
A ce t . ac i d . p
R e d ru s Po t . a c e t at e .
s ia t e . t r it e s ia t e
.
quite dark brown in color although the ferrous salt solution is pal e
,
green and nitric oxide colorless The com p ound which is formed .
here has not been isolated but it has been shown to consist of
,
p e r sec
. against an incandes cent N ERN S T filament 2 9 1 ) N O is
formed ; a more ra pid current gives oz one .
latter takes u p exactly half the volume of the ori ginal gas The .
N 2 0 4 T—f 2 N 0 2 , ‘
1 v ol . 2 v ols .
the fact that not only can the degree of dissociation be e s timated
from t h e intensity of the color but that it can even be measure d ,
— =
P x hx2
,
with alkalies nitrous and nitric acids are formed ; we may therefore
,
1\ 8
5 9
> o H
+ zo = N O 2 O H+ N 0 O H ~
.
Nit r ic a c i d . Nit d
r o us a c i .
b le iodides .
The com position of n itr ogen dioxide follows from its synth esis
eq uation 2 N O H O 2 an d from t h e va po r d e nsity
‘
.
, ,
O xy g en Ac i ds of N itr o gen .
O nly cert ain ones of the ab ove nitrogen oxides can b e regar d e d
as aci d anhyd rides The pentoxide is undoubtedly one an d the
.
3 HN O 2 = HN 0 3 + 2 N O + H2 O .
aminic acid However no one has yet been able to obtain this
.
a ci d fro m nitric oxide and water The same is true for nitrous .
Hypo n i tr o u s A c i d, H2N202 .
m ethyl alc oho lic solu t i on of hydroxyl amine Th e free a ci d does not
-
.
ac i d i s form ed .
are k nown .
02H50 N 0 2 N HzO H Cs O H ‘
i ‘
H2N 20 3 o
Et h y l Nit r at e
The alc ohol ateis a dded in order to c on vert t h e free a ci d d ire c tly i nto its
sod iu m sal t If the atte m pt is m ade to li bera te i t by addi ng a s t ro nger
.
2 N 3 2N 3 0 3 “
“
2 N 3 N 0 2 i N azN 20 2 .
NI TR O US A C I D, H N 0 , .
2K N 0 3 2 KN 0 2 02 .
1 90 IN O R G A N I C C HE M I S TR Y . 1 27
because this makes the residue easier to remove from the reto rt .
las t b o ttle c onnects with a cok e towe r thro ugh which wat e r is
FI G .
—M ANU FA C T URE or N I T R IC A CI D .
tem perature the acid sodium sul phate that is formed acts on t h e
second molecule of n itrate also forming nitric acid :
,
N aN 0 3 N aHSO 4 N a2 SO 4 HN 0 3 .
time as follows :
2HN 0 3 2N O 2 H2 O O
r eaches a diamete r o f 2 m in .
I nstead of b roa d ening out the electric arc t o a sun sha ped dis c -
turne d on the arc forms at the first instant in the l ower par t
,
into the pipe so that the arc comes to o c cup y the p ortion of
,
p roduct ,
for it diss o ciates at ab out 6 00 into N O an d 0 2 With
°
.
N2O 4 H2 O HN 0 3 HN O 2 .
more concentrated :
2 HN O 2 H2 O NO2 NO .
I N O R G A N I C C HE M I S TR Y .
I§ § 1 27
acid o n the metals is not the same in all cases I t d oes no t attack .
gold or platinum Sil ver mercury and co pper are only im per
.
, ,
dissolve with the evolution of nitric oxide This and the other .
above named metals for nitric acid which is per fe c t y free from
-
them does not dissolve these metals while the reaction immediately ,
iron filings and dilute sul phuric acid the reduction of nitric aci d
to ammonia in d ilute solution is quantitative There are also .
the sul phur is conv erted to sul phuric acid similarly phos phorus to ,
The com pos ition of nitric acid can be deduced from that of its
anhydride A weighed amount of the latter is introduced into
.
arts by weight of barium oxide B a O comb ine with the an hyd ride
p , ,
.
( = O
It is found that p arts 1 B a ) combine with
p arts 1 N 2
O 5) of the anhydride ; t h e formula of barium nitrate
i i c Ac i d HN O
Pe rn t r , ,.
Pern i trica ci d has the v ery c h ara c teri st ic pro perty of liberat ing bro mi ne
fro m potass ium bro m i de so lu t i ons so m ething that ne i ther hydro gen
,
2 80 2 N 20 4 + O Hg O Q SO 5 N H .
S0 2 HN 0 3 SO 5 N H .
SO 5 N H H2 O H2 SO 4 HN O 2 .
ture SO 2 < 83 can be ascribe d to sul phuric aci d ; to nitrous acid the
s tructure HO N O
-
s inc e a hy d roxyl group is assumed
,
1 29) to
e x is t in i t For the chamber crystals we therefore hav e
.
OH
n itrosyl ,
Sinc e t h e atomic grou p N O is known as the rational
n ame for the com p ound is n itr o s yl s u l phu r ic acid .
1 96 ,
I N O R G AN I C C HE M I S TR Y . 1 28
n itr o so s u l ph o n i c a c i d
-
HN O , + so, = O N so,H,
which is very unstable however and unites at once with a , ,
O N S0 ,H HN O , ON /
\ So, H
but the nitrosi sul phonic aci d likewise very unstable so on s plits
-
, ,
ON
< s o, H
acid :
2N O O H,O 2 HN O , .
“
”
the sul phuric acid factory and is cal led nitrated acid o r
O n d ilution with water th is Solution is n o t
”
nitrous vitriol .
851 8g
0
2 s0 2 2R 20 80 2 3 s0 2 + 2N o
O THER N I TR O G EN C O M PO UN D S .
Upon mixi n g c on c entrated so l ut i ons of sod ium n i tri te and sod ium
b i s ulph i te the liqui d heats strongly and a react i on ta k es place a cc ord i ng
to the fo ll o w i ng e qu at i on
N aN O , 3 N aHSO 3 N ( SO sN a) 3 N aO H HZO .
po tassi u m im ido su l ph o n at e
N ( SO 3 K ) 3 “
1 H20
”
N H ( 80 3 K ) 2 “"
i KHSO 4 .
If the boi l ing is continued for a l ong period , am ido su l ph onic acid is pro
du c e d
2 H,o = N H,so,H K, so, K HSO , .
Si mil ar
derivat ives of hydro xylam ine are al so kno wn The potassium .
,
-
+ 2 H,
0 = HO N H,
2 s o,K H .
PHO S PHO R US .
1 99
—
t i on of col d sat urated potass ium c hl ori de so lut i on c auses t h e separat i on of
orange c rystal s of the c orrespond i ng potass ium sal t wh i ch i s al so so l ub l e ,
i n water wi th a Vio l et c ol or .
p owdered g l ass or the lik e I t i s imm ed i ate l y bro ken u p by alk ali es
.
PHO SPHO R US .
de posits ; other phos phates which are frequently met with are :
3 C a3 ( PO 4 ) 2 + C aC 12 or C a ) v ellit e 4 A l P O4+
a pa tite , ( ; w a ,
p hos p hate .
Gy p sum .
On being heated this phos phate loses water and is converted into
calcium metaphos phate :
C HH4 <PO 4 > 2 C a ( P0 3 ) 2 2H2 0 .
The latter [ or in some pro cesses the original phos phate material ] .
is mixed with p owdere d coal and sand and reduced in a con '
d istils over :
Fin ally the p hosphorus is c ast int o sticks and in this form enters
the market .
1 3 2 . Ph ysical P op er ties
r —A t or d inary tem peratures phos
.
°
The v apor den sity of phos phorus at temperatures between 5 1 5
an d 1 0 4 0
°
is —4 50 I t s molecular weight is there
fore I nasmuch as the smallest amount of phos phorus that
is found in one gram—molecule of any of the numerous phos phorus
compounds investigated is 3 1 g this number therefore re presents
.
,
02 IN O R GA N IC C H E M I S TR Y .
the red phosphorus vari es between and a cc ord ing to the d u rati on
and tem perat u re of the heat i ng I t i s probab l e that i t represents a
.
Sul phuri c acid when warmed with it is reduced t o sul phur dioxid e ;
, ,
nitrate for instance gives silver and silve r phos phide A g3 P with
, , , ,
are very mysteri ous The o xi dat i on and hen c e the l uminosity is
.
, ,
666 m m fo r .
,
and at 7 60 mm for The o xi dat i on i s there
.
dil u te gas .
The fa c t that o xi dat i ons are m ore energ et ic u nder red uc ed oxyg en
press u re has been ob ser ved i n m any other c ases Se e 13 7 . .
—
water in a distilling fl ask connected with a condenser by a tub e ,
“
m a t c h e s Th e m at ches in u s e to day m ay b e cl assed as safety matches
’
-
,
-
substi t u tes The red phosphorus and phosphoru s ses qui s ulphi de
.
”
-
C o m p o u n ds of Ph o s ph or u s an d Hy dro gen .
( ) q
2 l i u id hydrogen p hos p hide P2 H4 ; and ( 3 ) s o lid hydrogen ,
b ringing phos phorus together wit h z inc and dilute sul phuric a cid ,
4H3 PO 3 “
PH3 i 3 H3 PO 4
'
.
P h os p h o r o us P h o s ph o ric
ac i d . a c l d.
Th e o r d in ary metho d of re
p p aration is b y t h e a c t ion of phos
ph o r us o n ca u stic potash :
P4 3 KO H 3 11 20 PE 3 3 H2 K P0 2 .
Po t h po p h o s
p
.
te .
The r ,
for in addition hydrogen P21 1 4 and other substan c es are form ed (See
,
4
.
al so
2 06 IN O R G A N I C C H EM I S TR Y . 136
was describe d in 2 9 .
liquid at —
8 5 and solid at °
It has a p eculiar disagree
able o d o r that reminds one o f s poiled fish I t is slightly soluble
,
.
g at O an d 7 6 0 mm p ressure
.
0
. .
2 PH3 40 2 P2 0 5 3 H2 O .
PHs 02 H2 PO 2 H,
M e t ap h o s
p h oro u s a c id.
if the gases slowly d iffuse into each other in a d ilute d con d ition .
reaction is decidedly sim ple and that chemical processes are almos t
always mono or bimolecular A ccordin gly when the quantita .
,
p ound ,w hic h is formed when dry hydrogen p hos p hid e and hydro
gen i odide are mixed In conta ct with water it brea ks u p into
.
PH3 and H I ; the former esca pes as a gas while the latter remains ,
d issolve d in water .
com pletely disso ciated into the t wo hydrogen com poun ds PH3 ,
and HB r as low as
,
Phos p honium chloride is disso ciated
even at o rdina ry temperatures and pressures and can only exist
below 1 4 or under more than 20 atm pressure C onsidering
°
. .
general behavio r of the latter thus shows that it is very much less
basic than a mmonia .
p h o r u s trichloride .
The co pper combines with the phos phorus so that the increase ,
in weight of the tube shows the pro portion of p hos phorus The .
2 PH3 3 H2 2P .
2 v ol s .
3 v ol s . s o l id.
,
— ° °
.
and has a spe cific gravi ty of It is eas ily de c o m posab l e and can
not be preserved be c au se i t rapi dly c hanges to the gaseo u s and the
,
li
So d Hydrogen Ph o sph de , i
1 39 Thi s substan c e i s form ed by the de c o m pos i ti on of the precedi ng
.
I t is i nso l ub l e in water .
2 10 I N O R G A N I C C H E M I STR Y .
141
p h or u s trichloride Fine
. l ight yellow crystals
-
at once a p p ea r and
the entire mass finally becomes solid indicating that all is con ,
mois t air being imme d i ately decomposed by water with the forma
,
almos t colorless takes on the yellow color of chlorine for the ab ove
,
PCl 5 H2 O PO C l 3 2 HC l .
With more wate r pho sphoric and hydro chloric acids are produced .
—
1 0 013 4
3 -
11 01 .
1 43 These are very anal ogo u s to the chl orine derivatives They are
. .
addi ng one to the other and then d i st illing o ff the so lvent The flu ori des .
hav e spe ci al m ethods of pre parati on A l l these c o m po unds are bro ken
.
q uite sl owly .
O xyg en C o m po u n ds of Ph o sph o ru s .
44 Three
1 com poun d s of this class are known : phosphoru s
.
importance .
to the pentoxide .
i
Ph os ph oru s Tetr o x de , P20 4 ,
co l orl ess gli stening crystal s that break u p i n water into phosphorous
,
This com poun d is the product of the c ombustion o f phos pho rus
in oxygen or an excess of dry air I t forms a white voluminous .
, ,
snow like mass that takes u p water rapidly to produce phos pho ri c
-
line subliming at
,
the other amor phous and not volatile
below red heat ; the va p or condenses crystalline When heated .
A c i ds of Ph o sph o ru s .
1 . O nly
two of the above described oxides of phos phorus
45 ,
we have :
21 4 I N O R GA N I C C HE M I S TR Y . 1 45
,
. .
, ,
M51 0 6 et c
,
These c an be derived fro m a h yp et ical a ci d I ( O H) 7
.
fro m I (O ) 7
H — 2 H, O ; and M I O 4 fro m I ( O H) 7
— 3 H, O .
1 46
This acid can be obtained by direct synthesis from its
.
elements ; phos phorus burns to the pentoxide and the latter yields
the acid on dissolving in water Its formation by the action of .
amount of dilute sul phuric acid formin g calcium sul phate which , ,
is only slightly soluble in water and phos phoric acid which goes , ,
into solution O n eva porating this solu t ion the acid remains
. .
. I t generates .
are p ossible and known to exist ; these are the pr i m ary, se c o n dary
and t e r ti ary salts O f the alkali salts all three kinds are soluble ;
.
of the alkaline ea rth salts only the primary the tertiary and ,
This latter pro perty is due to the fact that phos phoric acid is
a w e ak er acid than the strong mineral acids hydrochloric nitric
'
, ,
the more the association since the hydrochloric acid reduces the ,
with tha t of the metal ions presen t to reach the value of the solu
b il it y product ; hence all the phos phat e must dissolve
For the same reason a s a gen er al r u l e sa l ts that are insolu ble
, ,
—
forming mainl y the pyro acid but also a little meta acid through -
out the react ion The pyro acid on the other hand is converted
.
-
reaction
N a2 HPO 4 + 3 A g N 0 3 = A g3 PO 4 + 2 N aN 0 3 + HN 0 3 ,
o r, expressed in ions
HPO ”
3 Ag A g3 P0 4 + H
i
)
4 C .
"
t at io n is practically com plete .
acetic acid is only very slightly ionized and its ionization is more ,
.
216 I N O R GA N I C C HE M I S TR Y 1 46 .
p ossible ,
and the direct reaction must t herefore become com
p l et e ,
or in other words all the phos phoric ,
acid is p reci p itate d
as silver phos phate .
I t was stated above that the alkali salts of phos phoric aci d
are soluble in water These aqueous solutions differ markedly
.
fully explained .
is ca pable of s plitting u p into the ions H and HPO 4 the former ” '
“
In this case H2 PO 4 beh aves as a weak acid Hence if there is
’
.
,
”
a large pro p ortion of HPO 4 ions in a solution they will tend ,
.
,
reaction .
for phos phoric acid is that in nitric acid solution a finely crystal
line yellow preci pitate is produced by ammonium m olybdate
,
,
b o iled in aqueous solution it goes over into ortho phos phoric acid .
the meta acid can be distinguished from the ortho and the pyro
-
ac ids by its ability to coagulate albumen and give white pre c ipi
tates with chlorides of barium or calcium .
, .
of t h e a ci ds H4P40 1 2 and ,
OH HO OH OH
O PO H HO P O PO H PO H
|OH mo 0
P h os p h o ric Ph o s p h o r o H y p ph p ho os o ric
ac id . ac i d . a ci d .
PHO SPH O R O Us A C I D .
9
M e t a ph o s ph o r o u s A c i d, HPO z .
PH3 02 = H2 + HP0 2 .
vapor .
PHO SPHO R O US A C I D , H3 PO 3 .
P013 3 H 2 0 = H3 P0 3 3 HC l .
m i xed .
p olybasic acids sometimes a ffects only one If ion at first the othe r s ,
”
it may be supp osed that ionization beyond 2 11 and HPO 3 is in
°
p hos p hites are not oxidized by the air but they yield t o the action
,
of
2 20 IN O R G A N I C C H E M IS TR Y . 1 52
—
o xidizing agents the y liberate the prec ious metals fro m
’
; e .
g .
into hydrogen pyro phos ph ates and phos phide The double , .
1 52 . Sa lt s
th i s aci d are produc e d
of b y h e at ing ph o sph or u s w ith c au st ic
so da ,
l ime—w ater or b aryt a w ater -
3 B a ( O H) 2 + 8 P 6 H 20 3 B a ( H 2P0 2) 2 + 2 PH 3 .
Th e e qu at i on are : s
t u e s I n t h e s e re a c t i ons t h e a ci d i t s e l f is c o n v ert e d i n t o p h o s p h or ic
p e r a r .
b as ic .
C om po un ds of Ph o sph or us an d Su ph url .
53 1 i o u s c o.m pVar
o u n d f t h i o t a e k o w n ; a l l of t h em s e o s s r r n ar
Th e c ompo u d P 8 w h ic h i f e vic in o g
n 2 ic ch emi t y i ye ll w
5,
s o s r e r an s r ,
s a o
w a m d w ith w t r i t y i l d p h p h r ic
r e a e ci d d ulph urette d h ydr g e s os o a an s o en .
P S n it e w ith 3 m l e c l
2 5 u
s f K S t f rm lp h ph Sph t K PS i e a
o u es o z o o a su O O a e, 3 4, . .
p h p h
os t e w h e o
a x yg i e p l c e dosb y l p h u r en s r a su .
S ver l c mp u d c t i i g
e a o h lo g i add it i n t ph ph u a d
o n s on a n n a a en n o o os or s n
s ul ph u k w r g FSC l
ar e Th i p h p h
no n, e l p h h l id
. . b p 3 . s os o ru s su oc or e c an e re
A rseno pyrite yields arse n ic on mere heating the latter sublim ing , .
2A 8 2 0 3 60 AS 6 00 .
Va p or D en s ity .
—
The lemon yellow v a por of arsenic has a
-
A s ga 3 H2 80 4 = 2ASH3 3 ZII SO 4 .
disagreeable odor .
It is an endothermic compound ,
As + 3H — As H3 C al ,
A s H3 6 Ag N O 3 A s A g3 3 A g N O g .
fil te r paper and the m o ist spot i s he l d over a test t ube c ontai ning so me -
A r in e — If
f
C om pos ition arsine is passed over hot co pper
o s .
, .
De t e c t ion of A rsen ic .
are st ill u sed tho ug h muc h less than form erly i n dye ing tapestr i es
, , ,
fre quent ly c all ed u pon to analyz e a given sam ple (of dyed m ater i al s
or the like or the c ontents of a sto m a ch) for arsenic Fo r th i s pu r
, .
chl or i ne has been e xpelled by warming and the liqui d has been filtered ,
the liq ui d to be tested for arseni c The least tra c e of the latter reveals .
arsenica l gases .
, ,
—
having a s pecific gravity of )
( dZ I t freezes at 1 8 and
°
.
A8 20 3 GHC l fi Q A SC l g 3 H2 0 .
O xyg e n C o m po u n ds of A rs enic .
“
brick walled chambers where it collects as a white powder
-
Phy ical
s P r op er ti e s — A rsenious oxide is an odorless solid tha t ,
A bove this tem perature dissociation begins and at 1 800 the va por
°
'
for m i s better obta i ned by di sso lvi ng the vi treo u s m odific at i on i n water
or hydro c hl or ic a ci d and lett i ng i t c rysta lliz e out Du ri ng t h e c rystal .
of at ord i nary tem perat u res I f the l owe r hal f of a sea l ed gl ass t ube
.
grad u ally warm ed we have first a transform at i on i nto m ono clinic and
,
, ,
2 H3 As O 4 3 Hg O As zO 5 .
O xy ac i ds of A r sen i c .
A R SEN I O US A C I D , H3 A sO 3 .
1 61
This acid exists in the aqueous solution of the anhydride
. .
and not the acid se parates out This acid forms three classes of
.
,
.
The salts of the alkalies are soluble in water ; those of the other
metals are not but dissolve easily in acids however A neutral
, ,
.
A fter sul phuretted hydrogen has been led into a warm a c idu
lated solution of arsenic acid for some time arsenic is pre c ipi ,
The latter is also obtained by fusing arsenic trisul phide with the
required amount of sul phur I n the absence of air it can be
.
acids .
1 64
The trisul phide and the p entasul phide of arsenic dissolv e
.
A s zs3 i ““
3 K2 8 2 K3 A S S3 ;
Po t . sul ph
ar se n i t e .
A 8 2 S5 3 K 2S 2 K 3 A S S4 .
Po t . su l ph
ar se n a t e .
dride , e .
g
BaO + SO g = Ba SO 4 .
A N TI M O N Y . 23 1
A S2 8 3 K 2S3 2 K A8 8 3 .
Po t . s ul ph o
m et a -
a rs e n at e .
,
-
AN TIM O NY .
1 65 An t im o ny
. ccurs in natur e in stibnit e Sb 2S3 as w ell as
o , ,
1 .
11 . 2s o 3 + 3 c = 4 Sb + 3 C O z .
The crud e antimony thus obtained usually still con t ains arsenic ,
p etre the,
im p urities being oxidized .
P y ica
h l P — A ntimony is silvery white an d has a
s r op r ti s
e e -
'
-
p oint ,
M E N s C H I N G and V M E Y E R s u c c e e de d in d e t e r m in .
—
C hem ica l Pr oper ties A t ordinary tem p eratures the element is
not affected by the air ; when heated it burns with a bluish white ,
-
s e .
.
’
irn por t an t of these is typ e metal from which printer s ty pe is -
1 66 Stibine
is formed when nascen t hydrogen acts o n a solu
.
but contains 1 0 1 4 % Sb H3
— I f this gas mixture is p assed through
.
denses to a White solid mass that soon melts after the tube is ,
to be de posited .
, ,
-
The pr e .
SbC l 5 4 HzO
o
Hot water decom poses it into h ydgpc h l o r ic an d
.
p yroantimonic acids .
’
I t is ya light yellow crystalline p owder alm ost insoluble in ,
‘
water I t volatilizes at
. the va p or density at this tem
p e r a t u re corres p onds to the formula Sb 4 0 6 I t is insoluble in .
to the tetroxide .
and passes over into the hydroxide Sb O O H m eta a n tim on iou s a cid ,
-
.
2 Sb C l 3 3 N a 2 00 3 HgO 2 Sb O O H GN a C I 3 00 2 .
, .
O n the other hand antimony hydroxide dis p lays basic pro per
,
ties b y uniting with acids to form salts There are salts known of .
Sb ( O H) 3 as well as of Sb O O H
, E xam ples of the form er kind
-
.
this reason the group ( Sb O ) has been given the n ame an tim on yl ;
o n e of its salts is a n tim on yl s u l phat e ( Sb O ) 2 SO 4 The m ost ,
.
ta rtrate,
A N TI M O NY PEN TO XI DE A N D A N TIM O N I C A C I D
'
with concentrated nitri c acid and als o by decom posing the penta
chloride with water It is a white p owder almost inso l uble in
.
,
water and nit ric acid ; nevertheless when moist it turns litmus , ,
a
p p er red O n
. heating salt p etre w ith p owdered anti m ony the
p otassium sal t of m e ta a n t im o n ic -
acid K Sb O g is formed in an, ,
case of antim ony as in that of phos phorus we meet with three kinds
, ,
heating but resumes its original c olo r on cooling This tet ro xide .
Su l ph u r C o m po u n ds of An ti m o n y .
o range red p owde r which Splits u p in t o sul phur and the trisul phide
-
o f alkalies and their sul phides it dissolves easily with the form ation
o f s u l ph an t im o n iat e s M 3 Sb S4 ,
The best kno w n of these is s odiu m
N a3 Sb S4 + 9HzO
’
s u l pha n tim on ia t e , SC H L I PPE S It can
b e obtained b y boiling antimony trisulphide with sul phur and
caustic soda solutio n I t crystallizes in large colorless tetrahedrons
.
,
p entasul p hide ; even carbonic acid causes this hence the crystals ,
is not known .
BI SM UTH .
i
B s m ut h ou s o xid BiO is obta i ned by add ing an a lk ali ne stannou
e, ,
s
can heat the nitrate or carbo n ate or we can preci pitate the hydroxide
from the solution of a bismuth salt by means of a base and hea t
the pre cipitate I f a boiling solution of a b ismuth salt is treate d
.
with caustic potash the trio xid e se parates out in glistening needles
,
B i sm u t h i xi d
d o e, BiO ,, has been li ttl e studi ed ; i t i s a reddish yell ow -
p owder .
, .
i nto the c orresponding penta c hl ori de BiC l b u t produ c es the tric hl ori de , s,
BiC l an d free c hl or i ne
, .
Hy dr oxi de s an d Salt s .
1 73 . B i sm u th h y dr oxi de , Bi( O H) 3 , is
obtained by p reci pitating
a bismuth sal t with an alkali I t is an amor phous white powder .
,
over into the com pound BiO O H with the loss of a molecule of -
BiO O H basic
-
.
addition of much water converts it into the basic n itra tes several ,
“
+ Bi( N 0 3 ) 3 This is the b i s m u th s u bn itr at e , which
”
is used in medicine .
Su l ph u r C o m po u n ds .
in alkalies and their sul phides hence forms no sul pho salts Whe n ,
-
.
S UM M A R Y O F T HE N I T R O G E N G R O UP .
relation shows itself even in the formula types of their com pounds .
ro
p p erties This is shown by. the following small table :
A to mic w igh t e . 31 0 .
( Wa t e r 1) li q ui d
M lti g po int 8 00
° 0
e n -
. + 44 4 ca .
Bo ili n g po int
° °
-
1 94 4 27 8
Co l o r col o rl ess ye llo
w or re d gr y a
In
the chemical pro perties also regular variations are to be , ,
“
that the metallo id character g ives w ay to the metallic c haracter
‘
contrary dis plays a very feebly basic charac ter in arsenious oxide ;
,
since this oxide forms the trichloride with hydrochloric acid the ,
highest oxides of a rsenic and ant imony have s t ric tly acid pr op
e r t ies with b ismuth the acidic nature has practically d isa pp eared ;
,
the oxide B i2 0 3 has exclusively basic pro perties and the higher
oxide B l 2 0 5 ac t s like a p eroxide giving o ff oxygen readily ( it
,
excess of water .
ro
p p erties is very a pp arent C onsider the
. stability for exam le
p :
ammonia requires a very high tem perature for decom posi t ion ;
p hos p hine and arsine a much lower tem p erature ; stibine is unstable
at ordinary tem peratures when it comes in contact with oxygen ,
and the hydrogen com pound of bismuth is so uns t able that the
conditions for its formation and existence have not y e t been
ascertainabl e A similar change is noticeable in their ability
. ,
and Bis black The first three are sul pho anhydrides of sul pho
.
-
FI G . 39.
—A RT IFICIA L D I A M O ND S ( M A G N IFI ED ) .
at once covering the cavi t y with an iron sto pper When the Iron
,
.
enlarged v iew of some artificial s pecime n s ; they dis play the same ,
ro
p p erties as the rough natural diamonds p articularly the rounded ,
sul phur is fairly great at low tem peratures and the monoclinic
sulphur can thus exist only for a shor t time below its transition
point the transition velo city of gra phite into diamond is practically
,
has the effect of bringing the carbon into the region of temperature
in which diamond is the stable modification ; it can therefore
s e parate in this form from its solution .
The e l e c tri c furna c e that M O I SS A N u sed for these and num erous
other e xperim ents i s very s im pl e i n c onstr uc t i on It c onsi sts of two .
FI G . 40.
— M o I S S AN s E
’
L E C T R IC FURNA CE (C R o s s -
S E C T I oN ) .
The last nam ed tem perat u re can howe ver only be m aintained for a
-
brief per i od as the uns l aked lim e soon m e l ts and fl ows like water A t
, .
'
Sp g = 2 09
. . . A s was stated above gra phite can be pre ,
addi t ion to carbon and called gra phitic a cid This subs t ance is
,
.
p olishes etc , .
( )
0 A m o r p h o u s C a rb o n — This is obtained in the purest state
.
remove the mineral m atter and finally heated re d hot in a curr ent -
tion of coal They conduct heat and electricity Wood char coa l
. .
from air ; the resulting black mass is treated with hydro chloric
acid t o remove the phos phates and carb onates p resent I t has .
,
. .
salts from liquids The charcoal obtained from the dry distilla
,
.
Peat and the various coal s owe the i r ori gi n to the sa m e geo l ogi cal
p ro c ess , the s l ow de c ay of pl ant r e m a i ns i n the absen c e of air
-
Peat i s .
trans i t i on c arbon d i o xi de and m ethane O H4 are g iven o ff and the res i due
, ,
be c o m es r i cher i n c arbon and poorer i n hydro gen and o x ygen than the
c orrespondin g c hief c onst i t u ent of pl ant t i ssues ce llul ose The follow , .
Ce llul o se
Pe at
Bro w n o ac l .
C ann e oalc l .
ci coal
A n th r a t e
The pl ants of wh i ch these for m ations ori ginally c ons i sted are di fferent .
M ol e c u l ar an d A to m i c W e i gh t of C ar b o n —Ch em i c al Pr o e rt ie s
.
p .
ato ms t o the molecule than amor phous c arbon and diamond more ,
than gra phite since gra phite and diamo nd are less easily attac ke d
,
m ar sh ga s -
H —
C 4 is p assed through a red ho t tube ethyl en e O 2 H 4
, , , , ,
of the latter is heated still higher (in the absence of air ) carbon
is deposite d We thus see that as the tem peratur e rises the num
.
to glow ; when fluorine was present in excess car bon tetraflu oride ,
C F4 was formed
,
.
, , ,
.
R a t i o b y w e i g h t o f c a r b o n t o o x y ge n i n c a r b o n di
oxide from the combustion of
N at u ra l graph i te 2 999 4 8 0000
A rt ifici a l
Di a m ond
C o m po u n ds with Hy dr o gen .
“
”
It is an im p ortant constitu ent of n atural gas I t owes t h e .
”
name marsh gas to the fact that it arises from swam ps es pecially
-
“
when the decaying vegetation at the bottom is stirred u p I t
is called fire dam p b ecause it o c curs in c oal beds
-
fro m
.
l§ § 1 82
C + CO z = 2 C C .
C + CO z 2 2C O .
2 00 C 00 2 9
3 00 C al .
,
’
an elevation of temperature must according to LE C HA T ELI E R S ,
actually the case A s the tem perature rises the quantity of c arbon
.
°
monoxide increases ra pidly and at 1 000 there is still a very small
amount of dioxi de A t on the other hand practically all
.
,
This resul t is sur prising because the same chan ge should also
,
I I
. CO + O = CO z I f we assume that the second stage has an
.
unimolecular reaction .
C aC 0 3 Zn C aO Zn O CO .
2 1 4 and
O n accoun t of its tendency to combine with oxygen it displays ,
metals when hot Some com po unds are reduced by carbon mon
.
, ,
which can be isolated in the crystalline state but decomp oses again
very readily .
'
C AR BO N DI O XI DE , C AR BO NI C A C I D AN HY DR I DE, co,
1 84
This com p ound o ccurs not only by itself but also in com
.
extremely small cavities partly filled with liquid carbon dio xide
,
.
an d magnesia
2 N 3 H0 0 3 = N3 2C O 3 + H 2 O i 00 2 , 03 00 3
‘ ‘
00 2 .
d
So iu m b i
c ar b o n at e .
they are heated together with co pper oxide and the c arbon dioxide
formed is absorbed i n a weighed amount of caustic potash .
Sp g =
. 1 52 9 . I t is thus ab out half again as heavy as
.
,
°
at 0 u n der 3 5 atm os pheres press u re I t s critical tem perat u re is .
tween carbonic acid and its ions The result of this is that other .
. .
In the solid state also the acid carbonates give o ff carbonic aci d
gas very readily on warming .
1 v ol . l v ol .
K C O i s form ed at t h e anode
z z G, I n a qu eo u s so lu t i on i t set s free i od i ne
.
O th e r C arb o n C o m po u n ds
“
.
1 85 . C y an o gen , (O N ) 2 ,
can be pre p ared by heating mercuric
cyanide Hg (C N ) 2 or by treating a solution of p otassium cyanide
, ,
C yanogen
has a penetrating o do r Wh en liquefied it boils at .
e quatio n
C2N 2 20 2 2C 0 2 J
r N2 .
— —
C zN z l O z 2C O + N 2
'
r:
.
ie
. . a bimolecular p ro cess .
se c . I t is p l a i n th e re fo r e th at t h e s e c o n d v o lume o f o xyg e n i n flu e n c e d
, ,
Hy dr o gen
y an i de , HC N (pru s sic a cid) is im po rt ant in inor
c ,
s oluble .
FI G . 43 .
— R E V ER S E FLA M E . FI G . 44 — . PO T A SS I U M C H L O RA T E FLAME .
to the fact that at tha t high tem perature gaseous dec om position
products are formed which b urn If a gas burns
, in the air it
‘
is .
,
calle d a combustible gas and the oxygen of the air is called the s u p
p orter of the com b u stion These ex pressions in common. use are
Thi s can be eas il y obtained with the aid of the apparatus of Fig 4 3 . .
pr essur e i
, t s flame is st r ongly luminous incan d es c e n t gases . O the r ,
such as the va p ors of certain metals can rende r a flame lum inous ,
“
A gas fl am e whose light is due to incandescent p articles of car
-
bo n is made non lu m inous by mixing the gas with air before the
,
-
co m bus t ion This is the princi ple of the B UNS EN burner ( Fig
. .
which is used in all laboratories and quite extensively also with som e ,
. .
,
-
FI G 4 6 — E FF E C T
. . or A WI R E G AU ZE ON A F LA M E .
t am
s e is this amount of heat ough t t o r ais e the 18 g s t eam
. to
Fm 4 7 .
—
.Ma m a s cools o fi fresh portions of the gases unite
’
,
Their .
SA F E TY L A M P ’
FI G . 48 .
—Z O NE S L U M I N O U S FL A M E .
48 .
The narro w tube conducts o ff the inflammable gases and they
can be lit at the outer end .
across a flame ; the wire only g l ows a t the edges of the flame .
s ho w s The s ubstances i n burn ing illumi nat ing gas w h ich break u p
.
-
wi th the li berat i on of carbon are ch i e fly ben z ene and ethyl ene The .
the gas I f we assum e t hat the ben z ene i s com pl etel y bro ken u p and
.
2 62 IN O R G A N I C C H E M I S TR Y .
M 1 90
gen and some metals ; these s il icides have been pre pared main ly
by M O I SSAN in his electric furnace .
pe r a t u r e forming
,
sil icon tetrachloride an d silico chloroform I t -
.
Si 2 KO H H2 0 K2Sl O 3 2 H2 .
Hy dr o g e n Sil i c i de , SiH4 .
—
b ecomes liquid at 1 u n der a pressure of 1 00 atmos pheres I t has
°
.
esca pes from the ge n erat or forms a cloudy ring of hydrated silica .
Halo ge n C o m po u n ds of Si l i c o n .
1 9 2 . Sili c o n
t e tr ac h lori de SiC l 4 is pre pa red by heating Silicon , ,
hydrated silica .
Sl ii -
t h e a i r bo il s at
, and i s deco m posed by water .
, z e, .
2 03 F2 J
r 810 2 i H2 80 4 ““2
Sl F4 2 03 80 4 2 H2 0 .
action .
t iall y eva porated the residual liquid is able to dissolve silica becaus e
,
which silicic acid is dep osited because the excess of silicon tetra
,
FI G . 49 .
— PREPARA T I O N OF HY DR O FL U O S ILICIC A CI D .
b ubbl e of gas that ri ses fro m the m erc u ry into the water generates in
the l atter a c l o u d of s ilicic a ci d If the gl ass tube o pened direct ly in
.
into col d wate r at once without cracking They are atta cked only .
Sili c i c A c i ds .
with water and dried in the air it is a fine white amorphous p owde r
of the a pproximate comp osition Hg SiO g Freshly precipi t ated .
through the parchment b u t that the silicic acid does not T his
,
.
many of thei r salts and doub le salts are known which occur as -
minerals in na t ure .
o f the other metals insoluble as are also most of the double si l icates ,
o f the alkalies .
In t heso il hydrous s ilic ates are found whose bases are usu al ly lim e
and alum ina In c onta c t wi th alkali sal ts these u nderg o a do ubl e de com
.
g o u nd water
r This pheno m enon is sai d to be caused by the a bsorptive
.
”
The so l ubl e phosphates are absorbed by the so il i n the sam e
way Th i s i s m a inl y to be as c ribed to the lime they c onta i n wi th wh ic h
.
,
l
Si ic o n C om po u n ds of O t h er El em ent s .
9 5 Si icon
1 . l su l ph i de ,
SiS z,
is pro d uc e d w h en c rb on di ulph ide vapor
a s
is l e d o er a v mix t ur e of c c l
h ar o a a n d ilic t e d h t I t f m l n g
s a a r ea . or s o ,
s ilken n ee dl w h ic h
es, ar e b ro ke n up b y w ate r i n to SiO aq an d h ydro g e n 2
s ul ph i de .
Sil i c o n n it ride ,
SizN a, a white amorph ou s u b st n c e e pl t fro m t h es a , r s s
h e t i g o f s ilic on
a n in an at m o ph ere o f n i tro g en
s ( Fo r metal s ilici de s f. c .
I N O R GA N I C C HE M I S TR Y .
196 .
C O LL O I D S .
s ide r able number of such sub stanc es is now known and the ,
of small diff usibility G radually the vie w develo ped that the
.
, ,
trioxide solution is first a cidified with a little hydro chlo ric a cid
( a highly ioni z ed sub stance ) the A s
, 2 S3 se parates out a s a yellow
p reci p itate .A gain we
,
may take mercuric cyanide a c om p ound ,
r etained in c ollo idal solution ; yet the usual p recip itate can b e
,
a ci d
.
270 I N O R GA N I C C HE M I S TR Y .
1 96 .
its va p or tension does not differ perce ptibly fro m that of p ure
water When however a certain stage of dehydration is rea che d
.
, ,
C rystalloid salts for exam ple diffuse in them —e ven in the con
, , ,
—
gealed mass almost as easily as in water If a p iece of j ellied .
,
agar agar is immersed for some time in a dark blue am monia cal
-
—
solution of a co pp er salt the agar agar becomes s t ain e d t h ro u gh
'
—
does not p enetrate at all into the agar agar a s ab ove The ,
.
p h id e s hydrated
,
oxides etc M ost of them are mobile
,
liquids
.
,
71 mill e quivalents of N a Cl
-
p e r liter ,
of M gC l z and
Of Al C l g .
but the hydrosols of gold and arsenious sul phide mix without
p reci p itation These
.
p henomena have been shown to be connected
with the behavio r of the substances toward the electric current .
to the ano de o r to the cathode A t one of the two ele ctro des an
.
aqueous layer a ppears which is entirely free from coll oid and is
,
tion exists in this case between the colloid and the solvent .
so soon as dust pa rticles enter the air the path of the beam can ,
that many reversible col l oids are extremely fine emulsions ; for
instan ce an emulsion like a gelatine solution cannot be coag
, , ,
“
,
E I N ST E I N PERR I N
,
SV ED B E R G and others have shown that
,
colloids j ust like t rue solutions are subj ect t o the o smotic laws
, ,
.
27 A IN O R G A N I C C H E M I S TR Y .
G erm an ium x
dio ide , G e O z, is p r o d uc e d b y h eat in g t he corre p di g s on n
h ydro xide or b y r t i g t h l m t it ul ph i d o b y
, o as n e e e en or s s e r tr t i g i t w ith
ea n
i u
s na ffe c te d b y h e t a .
h yd ge
ro ul ph i d i p e d i to t h e lut i
n s f g e rm
e ium d i xi de i
s as s n so on o an o n
str on g hydr ch l ric ci d I m i t i it d c mp s givi g ff h yd g n
o o a .
'
n o s a r e o o se ,
n o ro e
Fo g erm an ium cf al o
r 218 . s .
TIN .
ties are on the group of islands lying east of Sumatra ( B anca Bil ,
liton Sin k O p
,
There the metal occurs in the form of t in
,
any sul phur or arsenic it may contain and then reduce d with car ,
again at a low tem perature and pouring it o fl from the less fusibl e
alloy of tin with iron and arsenic I t is then melted once mor e .
ally pure .
like etch fig u res are p roduced on the surface ( tin moir é e ) When t in
- -
.
Tin is very malleable and ductil e ; it can be beaten into very thin
leaves ( tin foil ) at the ordin ary temperature and at 1 00 it can be
-
,
°
drawn out into wire A t a very low tem perature and in contac t .
into another modification gray tin which has a lower s pecific gravity , , ,
TI N ,
27 5
A bove 2 0
°
this form changes back to white tin If the l atter .
passes so slowly into that form at ord inary tem peratures is tha t
the velocity of transformation is small in the neighborhood of t he
transition point ; it is accelerated on moving away from that point .
tr it i n po i t t e t ag o n al a h o m b ic i about
an s o n r r s
s o li d m e t l w a pl c d i a cyli n d r h vi g
as a e h l e i t h e b ott m
n d t hee a n a o n o , an
t h e t m p e r tur r c h d a b o u t
e a e ea T h i m a y b e t ak n
e pr f th at s e as a oo
it an b e e a ily p l veriz e d
c s u .
Sn 2 KO H H2O K zsn 0 3 2 H2 .
I N O R GA N I C C H E M I S TR Y .
1 99 . Us es .
-
On
account of its permanence tin is used as a pro
t e c t iv e covering for metals which are attacked by the air and t h e
”
above named agencies M any kitchen utensils are tinned
-
. Shee t .
and is then known as tin pl ate or sheet tin This is done by simply ,
-
.
Many all oys of tin are in use Solder consists of tin and lea d
.
re
p p ared by fusin g co pper with tin phos phide The result
ing mass is remarkably homogeneous and contains
hos horus and —1 5
p p 5 % tin I t s great hardness and firmness render
.
i p
t es ecially valuable for certain p arts of machines ( axle —bearings
) .
C o m po u n ds of Tin .
STA NN O US C O M PO UN D S .
the two C l atoms become ions ; they thus r equire two negative
charges ; but when these are form ed two positive charges are o b
t ain e d at the same time However the Sn "".
’
and C l ions unite ,
( f
c .
Mn 0 2 4H 4 Cl M IT 2 C l l 2 H2 O
“ O lg ;
' , ‘
, , '
the manganese and the rest serving to discharge two chlorine ions ,
St an n o u s h ydr oxi de , Sn ( O H) 2
is preci pitated when a s olut i on
o f stannous chloride is treated with soda
n ate e g
,
K zSn O g formed
. . The h ydroxide is also soluble in
,
.
They
_
.
ar e termed am ph o t e ri c c o m p o u n ds .
, ,
.
chl ori de are al so known The sul phate for instan c e is obtained by dis
.
, ,
so lvi ng the hydro xide or the metal in d ilute sulphuri c acid It form s a .
d issolve s t o form a ul p S —
when brought in c on tac t
ho stannate
with the p o l y s ulphide of ammonium or potassium Ks (x = 2 ,
811 8 K 2 S2 K 2 SIIS3 .
St ann ous s ul phide can also be pre pared by fusing tin with sul
phur I
. t t hen forms a bluish gray crystalline mass -
.
STA NNI C C O M PO UN D S .
, ,
Sn C l 4 3 HQ O the s o called
-
,
t in —bu tter A fresh solution of stannic
-
wate r has thus s pli t u p the stannic chloride into a basic hyd r oxide
an d an acid .
Su C l 4 PO C 13 Sn C l 4 SC l 4 e t c
-
I t combines with hydrochloric acid
-
,
.
,
,
-
,
KZSnFG which corres ponds to potass ium fl uo s ilic ate ; the sa lts of hydro
,
-
di ffer from each other b oth chemically and physically ; they are
c alled stannic and metastannic acids .
sium stannate solution This preci p itate reacts acid when moist
.
Stannic acid and the corres p onding chloride thus p as s over int o
the meta com pounds s p ontaneously ; on the other hand m e t ast an
-
i
Th e d ffer en c e b e tw een stann ic an d m etas tann ic acids w as po i nted o ut by
BER ZE LI U S as e rl y as t h e b e gin n i n g o f t h e n ine t eenth c entury
a Th ey ar e .
plic at e d c om p o s i t i o n s im il ar to t h e p o l y silic at e s
, fo r w h ich re as o n
m t as tann ic a ci d is regarde d as a p o lym er o f t h e ordin ary stannic acid i e
e ,
. .
,
th at it s mol ecul e is rep resen ted by (11 8 0 0 stan nic aci d i ts elf b e in g H Sn og
2 11 1 1 3, z .
28 2 IN O R G A N I C C H E M I S TR Y . 2 03
the brillian t surface of the metal protects the lead from further
attack by the air If however it is prepared in a very finely
.
, ,
of air it takes fire in the air even a t ordinary tem p eratures ( O ther
, .
a n d various veget able acids attack it ; Since all lead salts are very
p
_
io s o n o u s and very serious effects resul t from chronic p oisoning
with insignificant but succ essive amounts it is n o t admissible to ,
u s e tin containing lead in tin plating vessels for use in the kitchen
-
.
Zinc and iron preci pitate the metal from solutions A piec e of .
ie .
zinc is changed into the ionic condition and the lead ions are
.
,
discharged How it comes about that one metal thus assumes the
.
This emission of ions continues until the p ositive cha rge acquired by
the solution and the negative charge created on the metal balance
by their mutual attraction the tension ( called the el ectrol ytic
s olu tion ten s ion ) with which the ions are driven into the solution
-
.
Distilled water from which the air has been entirely removed
,
by carbonic acid .
Fro m a hygi enic standpo int these pro perties of l ead are of vast im por
tan c e be c au se dr i nki ng water i s a lm ost universally c ondu c ted thro ugh
“
-
, ,
m ost likely to d isso lve l ead The l ead eave tro ughs e t c wh ich were .
-
,
.
,
wi th an i nso lubl e l ayer of l ead s ul phate and bas ic carbonate (as well
.
absorbed by t h e water .
O xi de s of L e ad .
Pb 2 0 3 , Pb 3 0 4 , Pb O z .
cooling .
2 84 IN O RG AN I C C H E M I S TR Y .
a1 r .
lead nitrate and lead peroxide are formed henc e minium may b e ,
r egar ded as 2 Pb O Pb O z -
.
2 Pb C 12 C a(O Cl) 2 2 H2 O 2 Pb O z C aC l z 4 HC 1 .
O n warming it with sul p huric acid lead sul phate and oxygen are
-
,
p i n k sa l t
-
O th er L ead Sal ts .
concentrated sul phuric acid ; hence the crude acid which is con
c e n t r at e d in lead p ans 1 86 3 ) contains lead sul phate ; this is
,
”
L ead disu l ph at e , plumbic sul ph ate Pb (SO 4 ) 2 se parates fro m , ,
.
the acid around the anode when sul phuric acid of s p ecific
gravity is electroly zed between lead electrodes It has n ot been .
obtained quite free from lead sul phate I t is a white granular sub .
stance of stro n g oxidi z ing p ro pert ies Water de com po ses it readily .
int o sul phuric acid and lead peroxide I t is iso meric with l e ad .
p e r su l ph at e , Ps O g a salt,
of the dibasic p ersul p huric acid .
turns black if any hydrogen sul phide ( from drainage p i pes etc )
, ,
.
gets into the lungs Wh ite lead is particularly valuable for its .
and barite which are frequently substituted for white lead becaus e
,
“
siv e l y after the Dut c h m ethod Thi s c ons i sts i n pl a ci ng ro lls or
bu ckl es of lead pl ate into j ars c ontai ni ng a li ttl e a c et ic a ci d The
-
.
s ix wee ks the pl ates are alm ost ent i re ly changed to whi te l ead Th i s .
L e ad
l ph i de , Pb S is black and comes down amorphous when
su ,
SUM M A R Y O F THE CA R BO N G R O UP .
Bo ili g po int
n -
. ab o ve 3 000 °
circ a 1 500
°
1 52 5
°
28 8 IN O R G A N I C C HE M I S TR Y .
m 207
With re spect to t h e c h e mi c a l pro pe rties we n ote in t h e
'
first place that all th ese elem en t s h ave the same com p ound ty pes -
into the table of physical pro perties with its boiling an d m elt ing
points M oreover there is to be n o ted in ge n eral a transiti on
.
,
following facts :
1 O nly carb on and Silicon are known to form hydrogen com
.
in character in the cases of carbon and silicon and also in the cas e
of germanium while in that of lead the salts of the acid Hs O 3
,
are immediately de com p osed by water so that here the acid pro per ,
~
—
unaffected by cold water perha ps be cause of their insolub ility
in it ; the o ther halogen com p ounds MX4 are decom posed by , ,
water .
high ato mic we i ght I n the ni trogen group we saw it in the case of
.
b i smu th .
M ETH O DS O F DETER M I N I N G A T O M I C W EI G HT S .
2 08 . So
far only one method of determi n ing the atom i c weigh t
has been m entio n ed This consists in investigating as large
as p ossible a number of gaseous com p ounds of the element as t o
their va por densi t y and em pirical com p osition and then calc u lating
how m any grams of the element are contained in a mole of
the various com pounds The smallest figure thus found is taken
.
L iqui d .
Sp H °
. . at 2 57 pro
Boron . 0 2 54 11 0 . A m rph o us
o Sp H
. . . at 40
prod .
C arb on
m o rp h ou s
r
a
1d i am on d Abo ve 9 00
°
Sp H = 0 4 5
. . .
pro d .
So d ium
M ag e s
'
A lumi n ium
Silic on . C rys ta lliz e d . Sp H . . ab oy
prod
0
2 00 5 . .
Ph osph orus . l
Y e l ow . Sp H o f re d P
. .
pro d .
ul ur
S ph . R h o m b ic .
Po tassium
Ca lcium
c ium
S and .
C h romium .
M ang n es e a
I ron
Zinc
G llium
a
G ermani um .
A rs n ic
e
Sel e n iu m .
Bro mine
Zirconium .
M olyb d num e
R u th n ium e .
R h o d ium .
P ll dium
a a .
C ad mium .
Tin
im
A n t on y .
Tellu ium
r .
i
Io d n e .
um
L an th an .
ium
C er
u g
T n s te n .
Osmium
G ol d o o o o o o o
Th a llium .
L e ad
i mu
Bs th
um
Th o ri
C a ium
r n
2 09 ] M E TH O D S O F D E TE R JI I N I N G A TO M I C WE I G H TS .
R 12 ,
The law of N EUMANN l ikew ise holds for many elements
whose s pecific heat in the solid state has not been susce ptible of
measurement thus e g for chlorine compounds : for R C l com
,
. .
ato m ic heat found from the molecular heat of the com pounds is
constant but it is about
,
instead of about The same is
true of hydrogen whose mean atomic heat in soli d com pounds
,
ac c ord i ng to R EG NAU L T .
2 92 I N O R GA N I C C H E M I S TR Y .
209
The ato mic heat of s ulph u r i n c o m po unds is about and that of o xygen
ab o u t c onse qu ently t h e m ol e cul ar heat of t h e S0 grou p in i ts so li d 4
hav e fo und for the ato mic heat of t h e m etal a n umber muc h farther
fro m the a verage ato mi c heat of the el em ents than ,
2 10 3 Th e l aw of M it sc h erl ic h
. . The crys ta l form of com
.
the case of manganese suppos ing its a t omic weigh t t o be unk n own ;
,
p l c e a o th a t
, w sn t a f w f t h t mic w e igh t a e t b li h e d w ith
no o e o e a o s re s a s
ch emic l m t h m y b e e mpl y d
a e B th h ve b e n g e tly pe rf c te d
oas a o e . o a e r a e
gr aph s .
a e e
r n t i l to a n
sse ccu te d t rmi t i
a f n at mic w e igh t : ( ) A
a ra e e na on o a o a
( b) Th i c mpo u d mu t c o t i in dditi o to t h e l m nt u d r tu dy
s o n s n a n a n e e e n e s
fo e x m pl
r th t t h e s ub ta n c b e a mixtu e f t w t g
a e, a f o xi d t ion
s e r o o s a es o a .
( d) Th e c ompou n d e l e c t e d mu t b e ad pt d to n e x c t s ly i or e l e s a e a a an a s s, s
it s ex ac t yn th i from t h e w igh d l m e t mu t b e p
s es s ib l e e e e e n s s o ss .
re duc t io f t h e impu it i to a
n o p rt o f t h e w h ol r It w esf me rly a e . as or
n w w e k o w th t
o v y ub t c e th t e p r te out in a o li d ph se h s
n a e er s s an a s a a s s a a
s u b s t an c e c o t i e d i t h e ph e o u t f w h ic h t h lid e p a t d Al l '
n a n n as o e so s ra e .
i c h e mic l c o mb i at i o n
n a Ev t h e pl d i d gli t i g i lv r c ry t l th at
n . en s en s en n s e s a s
a e r b t i n e d i t h e e l e c tro l y i
O a nf a ilv it te luti d e pp re t
s s o
n l y s er n ra so o n an ar a a
n i trate m ay h ve i clu d d t c e s of N C l A g N O
a n N NO ve afte r a
e ra a or a n
, , 3 3, e
p ot a ium c h l i d
ss co t i n e ve rth el e
or e, f t h l tt
n ft r re pe ate d
a ns ss o e a er a e
re c yst lliz t io
r a O e o f t h e m o t t o u b l e o me o u r c e
a ns . n of ro in al l s r s s s er r
h e l d w at e r i c e i t i o t at all e
, s n y to d t c t b y c h e mic l t t
s n d c u es as e e a e s s an a s
it .
c ve rt
on c mp u d i t
on e oth qu t i t t iv ly T h m d i
o n n o t iga
an o er an a e . e o e rn n ve s
D E TE R M I N A TI O N O F E Q UI VA LE N T WE I G H TS . 2 95
p h a t e , e t c a r e n
. o t
,
s tr ic t l y i n s o lu b l e ; b u t th e ir s o lu b ili t
y h as fir s t re c e ive d
t t n t i o n in c o n n e c t i o n w i th t h e re c e n t a t o mic w e ig h t de te rmi n at i o n s
p ro p e r a e .
of method .
c o n c e p t s is th at o f t h e i de a l g a s w h o se e xp an s ion at c o n st an t p r e s s u e o r
, r
re ason 1 o f a n a c tu al g as at 0 an d 7 6 0 mm Hg c o n ta i n s a li ttl e
°
. .
w e ight o f t h e g as b e c o me s
a ir is s o me w h at l e s s fo r an e v a cu at e d glo b e th an fo r o n e fil l e d w i th g as .
t he a ir .
Th d t rmi e ti f t h q u t it y I c
e e b
na cc mpli h d i f u diffe t
on o e an an e a o s e n o r re n
w y a Wh ich a f u n d d c b d i t h l g r ph y ic m u l
s, re o I t h ul des ri e n e ar e s s an a s . s o
be n t d h w v o e th t th y h v o t y t tt i d t h x ct
, o e e r, a th t e a e n e a a ne e e a n e ss a
ch ct iz t h m th d f d t mi i g G I t h c
ar a er es e ef th l o ily
s o e er n n . n e ase s o e e s s e as
c d
on d ge n se li k H N O d C l h w ve r v ry ccur te d t mi at i
ase s , e , , , an , o e , e a a e er n on s
h v a l dy b m d
e a re a ee n a e .
Fr m exp
o im t l t dpo i t th e ph y ic o ch mic l m th o d h ve
an er en a s an n es s -
e a e s a
me u m t as re l y a e c a ri d t ft r t h g h a b
en s on b t i n d pure
r r e ou a e e as s een o a -
. .
All t h e u c t i t i th t
n i v lv d in ch mic l t
er a n f m ti
es s a e t h us
a ar e n o e e a r an s o r a on r
a v i de d ;
o a d u p n s uc h t n f m tio e v e ry p ur ly c h e mic al de t e rm i
o r an s o r a ns e
T HE PE R I O DI C SY ST E M O F T HE E L E M E N T S .
3 studying
2 1 the
. elements Inwhich we h ave considered so far ,
The questio n now arises whether all elements can be thus arrange d
into grou p s ; the re ply is a ffirmative .
t h e l m t i to g u p
e e en s f imil r e l e m t n DO E N R c ll d
ro tte s o s a en s . BE R E I E a e a n
a s arly e 1817 n d in 1 8 29 h e pr
as e te d t h e do c tr i n e
, a f t i d i e he es n o r a s, . .
s h o w d th t th ere
e d i ff t grou p
a f th ree e l e m nt e c h w h ich h ave
are e re n s o e s a ,
w igh t
e g Cl B I; C
s, e .S B . tc I n t h y r 1 86 5 t h e l w f o t es
,
r, a, r, a, e . e ea a o c av
M N D E FF a d L O T H AR M E Y ER lm t imult eo u s ly re ach ed c o n
e lu i
E
w h ich
s on s
EL E
e c o m pre h e de d b y t h e t e rm
“ n
pe ri dic syste m
ar
”
n
a os s an
o .
H 1
L1 7 Be 13 11 0 12 N 14 0 16 F 19
N a 23 M g 24 A1 2 7 1 . Si s 32
29 8 IN O R G A N I C C H E M I S TR Y . 213 .
H 1
Li 7 Be 9 1 . B 11 0 12 N 14 0 16 E 19
Na Mg A1 Si P s 01
Ag Cd 1 1 2 4 . In 1 1 5 Sn Sb Te I
Spo n din g pro p erties we are led to the su pposition that these
,
z
",
,
.
,
K 39 2 . C a 40 1 . Sc 44 1 . Ti 4 8 . 1 V 5I 2. C r 52 1
. Mn 55 0, .
N a 23 1 . Mg 24 4 . Al 2 7 1 . Si 2 8 4 . P3 1 0 . S3 2 I
.
THE PE R I O D I C S YS TEM OF THE E L E M E N TS . 299
at least so far as the valence and the form of the compound are
concern ed (A l g and Se gO g TiO z and SiO z K zC rO 4 and K 2 SO 4 , , ,
Cu Zn C a 70 Ge As Se B r 80 0 . .
N a23 1 Mg 24 4 Al 2 7 1
. . . Si28 4 PSI G
. .
L AR G E PE R I O D .
K3 9 2
. C a4 0 1 . Sc 4 4 1 . Ti4 8 1 V5 I 2
. . Cr 52 1 . M n 55 0 Fe 55 9
. .
N i58 7 . C u 63 6 .
~
Zn 6 5 4 G a 7 0. G a 7 2 5 A s 7 5 0 Se 7 9 2
. . Br 80 0
. .
As to the pos i t i on
of hydrogen in th i s t abl e opin io n s are d ivi ded .
che mic a l pro pert i es indic ate wi tho u t do ubt that i t be l ongs wi th these
metal s O n the other hand O R M E M A SSO N has presented argum ents
.
,
for pl a cing i t at the head of group VII as is done in this table These , .
t h e hal o g ens ; m oreover the bo ili ng po i nts of the alk ali m etals fa ll wi th -
3 00 I N O R GAN IC C H EM I S TR Y . 21 3 :
,
-
,
. .
,
s ubs tan c e .
” “
c a n re pl a c e hydrogen w i tho u t essent i a ll y a l teri ng the nat ure of t h e
h el iu m (at w t .n eon a rg on (4 0
. kr yp ton and xen on
it i s cl ear that they for m a nat u ra l gro u p for thei r pro pert ies displ ay ,
fro m t h e strongest e l e c tro ne gat ive to the stron gest e le c tro pos i t iv e
-
,
-
Very well .
G rou p VII I as has b een said owes its origi n to the setting
, ,
p pro erties
1 A l l these elements are of a gray color and diffi cu l t l y fusi
.
melting point of iron is higher than that of c obalt and the latte r
-
din ary tem peratures The former pro perty is especially developed
.
c om pound s O SO 4 and R u O 4 for exam ple are known and also those, , ,
e g Pt C 12 3 C C
. . In this last com pound platinum can also be con
-
.
s ide r e d o c t iv al e n t .
n ickel p alladium
,
and p latinum give
,
K-
2 R ( C N ) 4 double salts , .
6 They all form colored salts : those of cobalt are red or blue ;
.
the nickel salts are green ; all the rest are of v ar1 ou s sha d es of
b rown .
r eference to the large periods it is apparent that not all the ele ,
o nly those elements that belong to the even or the odd rows of
the large periods The s imila rity of the elements of these di visions
.
is seen in the case of the large periods from the following facts :
, ,
com poun d s .
p ro m i nent in the o dd ,
rows the acidic ro
p p erties .
t able , we meet first those that fo rm the strongest bases and then
gradually those that give acids The latter pro perty is most .
t h e Pe r io di c L aw in C o n st ru c tin g
'
Th e Us e of a Syst em of the
El em e n t s .
p p
ro er t ie s ,
is det erm in ed by the pos ition whic h it occu pies in the sys
t em and pa r tic ufla r l y j by the a t o m i c
o u r a d acen t el em en ts , the
a n a l o g u e s I f an element is in an even se ries the elements in
.
,
the adj oining even series are its atomic analogues ; the same is tru e
of the odd rows From this it follows that when the pro pe rt ies of
.
,
, ,
Thus beryllium would not fit in the sys tem with that atomic weight .
This is indee d its fit place i e its properties are those which must
,
. .
beryllium chloride .
beryllium and aluminium are very similar to each other ; they are
gelatinous and sol u b le in alkalies B o th metals are scarcely acted
.
u pgn by nitric aci d and both dissolve in alkalies with the evolution
contrast with the o ther me tals of the lithium grou p B oron and .
sil icon both form v ery refractory oxides and salts ; their fluo rin e
compounds are decom posed by water in a Similar manner etc ,
.
The e v iden c e in a cc ordan c e with which berylli u m was ass i gned its
p resent p os i t i on in the syste m was s u bse q uent l y c on fi r m ed d i re c t l y
by the determi nat i on of the v apor dens i ty of the c hl ori de whic h l ed ,
ASa second example let u s take thal lium This element dis .
pl ays analogy with the alkali metals and also with alu m inium as ,
3 06 IN O R GA N I C C HEM IS TR Y . 21 6«
the same way as we have Shown it for the oxides R 2 0 and R C it can ,
also be demo n strated that indium could not be located in the table
with an oxide I n O z I n g O 5 I n O g etc There remains thus no
, , ,
.
, ,
o ther possibility than to give the oxide the formula I n g O g and the
element an atomic weight of 1 1 5 .
for this p osition are cadmium and tin The oxides of both are easily .
the metals
A g , C d, I n , Sn , Sb (7 t h series) ,
we notice first that the melting p oint of Silver lies highe r than that
-
Ag > Cd ; Sn < Sb .
melting point o f these five metals This is actually the case ; its
-
.
melting poin t is
-
I n the color of the metals there is a further
analogy ; silver cadm ium and tin are white and so is indium As
, , .
Since cadmium is at the left and thall ium farther down in the system
as the following sets forth : the oxides of alum inium and tin b e ,
cause o i their slightly acid nature dissolve in alk alies forming defi
, ,
nite com pounds with the latter The oxi d es of cadmium and .
Finally there is also the con d uct of in d ium salts towar d hydro
,
gen sul phide which su pports the plac ing of the elemen t between
ca d mium an d tin for indium als o is , p reci p itated by hy d roge n
P r o p e r t ie s o f e k a s il ic on p di t d
re c e by P r o p e r t ie s of g e r m a n iu m dis c o v e re d by
M E N D E L EE F F W I N KL E R .
1 . Th e to mic w e ig h t mus t b e t h e
a 1 . At .
me an o f t h e four atomic an a
l og nes Si, Sn , Zn , Se , i e .
= 7 2 85
l ) . .
tw ee n th ose o f Silicon ( 1 3 ) an d
t in b t b e onl y a trifl eu
ab o ve 1 3 .
mus t b b l to fo m lkyl m
e a e r a co G e ( C , H5 ) 4 b o ils at 1 60 an d it s
°
at
7 . Sn i ce t he o x i de s
indium n d of a 7 . il
G e O 2 is e as y re d e d to t h e e ta) uc m
rs enic a
a as il y r d uc e d
re th i se e ,
by h eat n w th i g
ar b o n o r in i c
mus t als b e t ue o f E8 0 o r 2 . hy dro en g .
8 . E S b c a use f it s a n l gy w ith
S 2, e o a o 8 . i lv
G e S2 d ss o es read y in N H4SH il .
Sn S w ill p o b ab ly b s lu b l e n
,, r e o i
N H SH .
9 E s Cl i s
. u d liq i
b o s b e o w 1 00
°
,
. il l G e Cl 6 is liqui d , b oil s at an d
( °
s n e ti c
h e b o n — o nt o f SiC l is
p 4
ili g i h as a s pe cific g ravit y o f
5 7 a n d t h at o f an d
h as a s pe ra cific g vi
ty o f 1 9 . .
1 0 K,Sn F6 b e n i gm
o r e re a d y s o b e il lu l K2 SiF, is al m o s t i n s o lub le
K, G e F6 di ss o lves m 3 4 p art s o f
. .
in Wate r th a n K2 SiFe t h e s o ,
lu
bil it y o f K, ES E6 s t a so b e mu l bo ili g w t r
n a e .
greate r th an th at o f K zSt .
3 08 I N O R G AN I C C HEM IS TR Y 21 8
2 1 8 In
the grou p of the platinum metals the atomic weight s
.
firs t of the three on account of its analogy with iron and ruthe nium ,
by SEU B ERT Showed that in reality osmium has the atomic weigh t
1 9 1 iridium
,
an d platinum which order is in harmony
V ith the system .
2 1 9 G r aphi c r e pr ese t ti o
. n a n — The fact that an arrangement .
through the period (in the large periods at grou p VII I ) and then
incre ases again I n the descen ding portions ar e the ductile on
.
,
—
electro p ositive on the ascending the electro negative elements -
.
, ,
t he u nity o f m a tte r .
t h e i r ato mic w e igh ts l e ads u n avo i dab ly to t h e ass umpt ion o f a pri mor dia l
o r gr o u n d su bstanc e As to t h e nat ure o f th i s s u b s tan c e n o e vi de n c e is at
.
LI THI UM AN D SO DI UM .
L ith i u m .
222. This m etal is not fo und free in nat u re ; in c o mbination how ever , ,
m in e ral w at e rs c onta i n i t
~
I t o ccurs c h i e fl y i n the s ilic ate l epidolite or
.
,
it be c o m es v ery br i tt l e and i ts s ilic ates are bro u ght into s uch a c ond it i on
that they c an be de c o m posed by hydro chl or ic a ci d The fine ly powdered .
burn s with an intense wh i te light to the oxide ; at ord in ary tem perat ures
it is not so readily oxi d iz ed as sodi um and potass ium It de c o m poses .
to c aust i c soda ; it d isso lves i n water produ cing a strongl y alk aline ,
so lut i on .
lith ium .
Th e lithiu m p s c on i s t
e c tr u m
s s of t wo re d b ands , o ne of wh ich in p ar
t ic u l ar is e asy to re c o gn iz e .
So di um .
22 3 . Sodium
oc curs in nature in enormous q u an t it ie s an d is ‘
and as a resul t of rock decay gets into the soil whence it enters
, , ,
the plants and finally reaches the animal organism The nitrate .
,
°
amm on i If
a e o f th
. e m t l
on i i t duc d i t liqui d mm n i
es e a sth s n ro e n o a o a, e
b igh t s u rfac
r f t h m e t l b e c om e t a n h d w i th
e o e n i n d ig o b lue c o l o
a s r
i
s e a -
r,
,
If .
3 12 IN O R GA N I C C HE M I S TR Y .
j 2 23
al s o l o s
e amm oni an d t h
a m e tal is left b ehind in t h e c rystallin form
e e .
b e in g form e d b e tw e en t h e m e t l a n d t h e mm o i b t th at t h ac opp r ed a n a, u e e -
r
c an b e pre s se d o ut l ea vi g a c om p c t p i c e o f m t l
,
n a e e a .
it kee ps its metallic lustre for days Sodium can b e heated in the .
ignites only when heated strongly whereu pon it burns with a very ,
, ,
O XI DE S A N D HYDR O XI DE S O F SO DI UM .
metal and after d istilling o ff the latter the oxi d e is left in the
crystalline fo rm I t is white ; it dissolves in water fo rming
.
,
c arried to com pleti on ; in practice the pro cess is inte rru pted
as soon as the alkali hydroxide concentration gets u p to
The caustic c athode liquid is then re placed by fresh brine and the
former is evap orated in vacuum p ans to a concentration of
whereu pon the undeco m p osed chloride se p arates out and is
returned to the electrolytic cell .
est closely against the outside of the dia phra gm and the c athode
c om p artment is filled w ith warm oil that is kept in lively cir
,
is em p loyed .
the two outside ones containing brine and the carbo n anodes ,
mercury c overs the botto m of the whole cell I n the brine com .
com petitive pro cesses the reader must refer to the technical
j ournals or the most recent works on industrial chemistry .
SALTS O F SO DI UM .
,
. .
,
from sea water and the water of salt wells Three metho ds are .
. . .
or sal t “
I n these the water is remove d by solar eva p oratio n
and th e salt crystalliz es out An y gy psum that may b e presen t .
and yields pure salt L ater on the other salts s e parate out ;
.
,
“ Th e
( salt
salt is obtain ed from this concentrated solution by boiling
C ommon salt is almost equally soluble in ho t
and cold water hence it does not crystallize out on cooling but fal l s
,
o u t at the same rate as the saturated brine eva orates even whil e
p ,
FI G 5 0 — G RADUA T I O N PR O C E SS
. .
.
’
Wh en a crystal of G lauber s salt is ex posed to the air it efil oresces ,
its saturated solution b eing l e ss than the mean tension of the wate r
va p or in the atmos phere I t is found that a perfectly s o und crystal
.
has begun at any p oint it Spreads over the crystal The phase rule .
p hases N a z S O 4,
1 0H 2 0 and H 2
-
0 ( moistur e of the air ) A ccordi n g .
sodium hydroxide and the secondary salt for the solution reacts ,
“
strongly alkaline and absorbs carbonic acid from the air The
”
ordin ary sodium phos phate is the d i s 0 d i u m p h o s p h a t e
.
N azHPO 4 1 2 H Q O
-
. I t se parates from its aqueous solution at
ordinary temp eratures in large crystals which soon effl oresce 1 00 .
p h o s p h a t e N a H z P O 4 H 2 0 reacts
-
acid ,
I t is converte d .
2 26
. So di u m c a rb o n ate , N a2 C 0 3 1 0H2 0 ( s oda s o l —soda ) is -
, , ,
This pro cess c onsists of three p arts I n the first place common .
I n the second p a rt of the pro cess sodium sul phate is heated with
coal and limestone The third section of the p ro cess consis ts
.
A fter the black ash has been leached out as far as p racticable ,
”
it is c ast aside as tank waste The m ost valuable constituent
.
which is then oxidi z ed to sul phur and the latter to sul phuric
acid The pro cess in its entirety is thus re presented by t h e
.
fo ll o wing equations :
2 N aC l Hg SO 4 N ag SO 4 l 2 HC l ;
= —
N ag SO 4 + 2 C
b
2 00 2 N ag S ;
N ag S C aC 0 3 C aS N a zC O 3 ;
C02 Hg O C aS C aC 0 3 Hg S ;
HQ S j“2 0 2
‘
HQ SO 4 ;
or summed
, up
2 N aC l C02 Hg O 2 HC l N ag C O g .
are wor ked u p N ev erthel ess thi s pro c ess wh ic h for a l ong peri od of
.
, ,
( )
2 The ammonia -
soda p rocess o f S O L V A Y .
p lace :
N aC l ( N H 4 ) H C 0 3 N a HC O g N H 4Cl .
—
solves in 1 0 1 1 p arts of water at room tem perature and reacts
alkaline O n being gently w armed it breaks u p into carb on
.
dioxide water and soda ; this dec omp osition occurs even on warm
,
ing the aqu eous solution and when a current of air is p assed ,
,
’
ways by fusing sand with G lauber s salt and charc oal This
,
.
mable text iles l ike theater dec orations etc ; it is also used for ,
.
filling Soaps .
PO TA SSIUM .
22 7 . C om p ounds
of p otassium occur in nature very extensively
but not in such large quantities as those of sodium Potassium .
exists prin cip ally in the silicates es pecially felds p ar and mic a , .
p ensable P otassium
. salts are also found in sea water The -
.
” —
s alts mainly double salts of p otassium and magnesium ,
, ,
- -
et c
. Th e la r g e amounts o f p otassi u m in th e felds p ars makes its
r ecovery fro m them a very enticing p roblem .
C O IlI PO UN D S O F PO TA SS I UM . 3 23
air ; when heated in the air it burns with an intense violet light .
being sufficient to ignite the esca ping hydrogen and drive the
p iece of p otassium around on the water .
O xygen C o m po u n ds o f Pot as s i u m .
which unites with water to form the hydroxide with the evolution
of much heat .
an d free oxygen .
sticks .
etc besides the c arb onate whic h is gradually formed by the action
.
,
the alc oholic solution is evap orated in a silver dish C aus tic soda .
state it greedily absorbs water and carb on dioxide from the air and
finall y deliquesces to a c oncentrated solution of p otassium carbonate ,
white mass of soda For this reason c austic p otash is a much more
.
Pot as si u m Salt s .
9
22 . r
Po t as s i um
lo i de ,chK C l occurs ,
at S tassfurt in the min
eral s yl vite I t crystalli z es in cubes and melts at
. I t is easily
volatilized at elevated temperatures 1 00 p arts Hg O dissolve .
re
p p ared by mix ing bromine with a p otassium hydroxide solution ,
of 1 3
'
ions in the latter c ase Th at the io dine has entered i nt o
.
from the fact that c arb o n disul phide takes u p nearly all t he iodine
from an aqueous solution of the latter when it is shaken with t h e
solution but o nly a small pr o p ortio n when the same o peration is
,
3 26 I N O R G A N I C C HE M I S TR Y . 22 9
sodium chlorate is much more soluble and does not retard the
electrolytic pro cess by se p arating from the solution as does ,
p otassium chlorate .
p art of the salt being at the same time c onverted into p ot a ssi u m
pe r c h lo r ate , K C l O a .
fo und i n c r u de C hili sal tpetre renderi ng the l atter unfi t for use i n
,
KC l N aN 0 3 KN 0 3 N aC l .
For this purpose hot saturated solutions of the two salts are brought
-
.
PO TA SSI UM S A L TS . 3 27
out on evap oration but when the solution is c ooled the saltpetre
,
c omes out first for it is much less soluble than sodium chloride
,
in c old water .
b orh oo d of the melt ing p oint the former is the stable variety
-
tion p oint of the two forms has not yet been determined 1 00 .
o btained solely from wood ashes these being soaked in water and ,
e xtensively from
p otassium chloride after the L E B L AN C p rocess .
t ories that c ontain s the p otassium salts in which the sugar beet is
,
-
rich .
cules of water of crystalliz at i on which form i s the only one s ui ted for
,
t h e abo v e rea c t i on .
H2 0 at the solut ion has a strong alkaline reac tion The salt .
Pot ass i um sili c ate , p otassium water glass is formed when san d-
,
.
water glass-
.
It absorb s o xygen from the air going over into the thio ,
2KgS Hg O 20 2 K 2 S2 0 3 —l 2 K O H .
KO H H2 S K SH Hg O .
KSH KO H K2 8 11 2 0 .
Po ass um
t i h
po ly l p i de s
su — When
a solution of potassium mon o
sul phide is obtain the c omp ounds K 2 S3
boiled with sul phur , we ,
K zS4 K zS5
,
A m ixture of these substances is also obtained by
.
“
fusing p otash with sul phur ; besides these it c onta ins the sul phate
and the thiosul phate and is called hepar su lphu ris ( liver of sul
hur because of its liver —
brown c olor These olysul hides are
p p p .
0 IN O R GA N I C C H E M I S TR Y . 23 2
R ub i d ium
o xi de when prepared i n t h e sam e way as N a O i s obtained
, z ,
0 an s i u m i s a s ilvery wh i te m eta l ; sp g m pt
-
b pt . . .
-
. .
-
.
I t soon ta k es fi re on e x pos u re to t h e a ir Th e o xi de 0 8 0 .
, 2 ,
The sal ts of c aesium are v ery Similar to those of r ub id ium ; som e of the m
.
p u re c aes ium c o m p u n ds
q Th i s i s p art icul ar l y tr u e of
. the p l at i n um
do ub le sal t already m ent i oned and t h e c aes ium a lum an d the a cid
-
tartrate .
SUM MA R Y O F T HE G R O UP O F A L K AL I M ETAL S .
3 The gradual
23 change of
.
the p hysical p ro p erties of these
metals with increasing atomic weight is made pla in by the follow
ing table :
A tomic w igh t e
Sp ecific g vity ra 0 59 . 0 97 1 52 1 85
M l ti g p i n t
° ° ° °— °
e n -
o 1 80 0 97 6 38 5 26 27
B ili g p oi n t
° ° °
670
°
o n -
the c arb onates and phos phates are soluble in water ( although in ,
d ifferent degrees ) the carb onates with basic reaction The metals
, .
O n the other hand we cannot overlook the fact that the metals
,
p otassium rubidium
,
and c aesium which are very similar to each ,
other di ffer from sodium and lithium in many res pects The last
, .
instance the first member of the fourth grou p which differs dis
, ,
t in c t l y from s ilic on and the rest in the ability of its atoms to unite
with each other ; also fluorine with its soluble Silver c ompoun d .
St ill other exam ples of this sort will be met with later .
, , , ,
o f its salts The sodium salts are almost all readily soluble in
.
, ,
hand and the other alkali metals on the other are entir ely dis
, , ,
s imilar .
Am m o n i u m Sal t s .
with the alkali group a descrip tion of a few amm onium salts may .
find a place .
c onduct the electric current very well this is not the c ase with an ,
a gas between a liquid and a vacuum while the other law has to ,
water for the quaternary base cannot be thus dec omp osed
,
.
s imila rly dr i e d amm onia gas and hydro chl o ric ac id gas do n ot
uni t e t o form ammonium chlori d e Traces of wa t e r t hu s
p ro duce a marked catalytical ac celerati o n b oth ,
of the formatio n
p h o s p h oru s p e n to xi d e .
( 2 ) C ar b o n m ono xi d e b urn s i n mo is t oxygen muc h
more e as ily th an in dry oxy ge n ( 3 ) Ve ry c are fully drie d de ton at in g
.
a s c an b e h e at e d in a t u b e to re d he at w i th o u t e x pl o d i n g
g
-
.
ous solution some ammonia esca pes acid sul ph ate being forme d , .
(
A m m o n iu m n itr at e N H4 N 0 3 deliquesces in the air ; when
, ,
it then loses amm onia and goes over into the secondary phos phate ,
( N H 4 ) 2 H P O 4 O n
. b oiling the solution the salt again yields ammo
n ia and is transformed into the primary phos phate .
p hos p hate ,
N a P 03 .
it smells strongly of ammonia and p asses slowly over into the acid
salt N H4H00 3 a white odorless p owder which is scarcely soluble
, , ,
in water This acid salt is also formed directly from the sesqui
.
the air (hence the o d or of ammonia) an d goes over into the first
named salt .
is ob taine d by satur ating aqueous amm onia with hydrogen sul phi d e ;
it is a c olorless liquid which soon turns yellow because of the for
,
p art of the hydrogen sul p hide and thus sets free sul p hur which ,
line m ass i s obtai ned whic h de c o m poses at ordi nary te m peratures i nto
,
N H SH and N H
4 The c o m po und N H SH separates o u t c rystal li ne
,. 4
SA LT SO L UT I O N S .
2 35 . Eve ry
solid substance is soluble in every liqui d ; howeve r ,
the pro portion which dissolves c an vary all the way from zero to
infinity I f only an infinitesimal amount of the solid goes into
.
—
already been demonstrated in many cases of so calle d insolubl e
substances E ven when we confine our attention to
aqueous soluti o ns of salts (includ ing acids an d bases ) we find t h e
336 IN O R G A N I C C HE M I S TR Y . 23 5
Wi th regard to the so lub ili ty of sal ts the foll owing pra c t ic al rul es are
worth re m e mbering : P o t a s s i u m s o d i u m and a m m o n i u m ,
n C l ,,
and — N or m a l s u l p h a t e s are so lub l e (e xc ep t those
p h a t e S and s
,
u l p h i d e s are i nso lu b l e ( e xc e pt those of t h e a lk a
lies) B a s i c s a l t s are insolubl e A c i d s a l t s are so lub le i f
— —
t h e a ci d i t sel f i s so lub l e .
p ressure I n the great maj ority of cases the solub ility increases
.
of absc issas and the amount of salt which dissolves in one hundre d
p arts of water is p lotted on the o rdinate axis a s o l u bility cu rve ,
l
i
very rap idly with the temperature ; for sodium chloride it remain s
p ractically constan t I n certain cases such as those
. of c alcium ,
hydroxide and c alcium sul phate (within certain limits of tem p era
ture ) the solubility decreases with rising temperature These .
the heat of s o lu tion i e with the caloric e ffec t which acc omp anies
,
. .
2 36 . Th eter m heat
f has v ario u s m eani ngs o We are obliged
s ol u tion .
to di sti ngui sh between ( 1 ) the c al oric effe c t of di sso lvi ng a sal t i n a very '
who le c al oric e ffe c t of disso lvi ng a sal t i n water u ntil the so lut i on i s
sat ur ated A S a rule these three m agni tudes will hav e di ss imilar
.
338 C HE M IS TR Y
'
IN O R G A N I C .
23 s
c ussed i t was beli eved t hat there were e xc ept i ons to the
, pr i n ci p l e but
,
, ,
‘
°
p roved to be at 1 4 it is abov e
+ 02 4 .
”
c omp onents is water than as water in which substances are
,
0
”
dissolved .
, ,
f
two degrees o f freedom We will supp ose that the s ol u t ibn 1s then
.
p hases ar e t h en
p
‘
resent the system bec omes univariant
,
We recall
that ch anges in the quantity of any phase have no e ffect on such
a system ; therefore if more sal t is introduced into the system
,
‘
This is none the less true when water is added or the vap or
volume increased so l ong as the three phases remain
, .
Th e o pini on was form erly hel d that at thi s po int a chemical com
p o u nd between the sa l t and water ( a c ryohydrate c a
‘‘
m e i nto e xi st
en c e That i t i s o nl y a m atter of mixt ures c an be seen in the c ase of
.
r equired B elow this p oint the s ol u tion can be r egarded as s atu rated
.
in which c ase also the solid phase goes into solution I f the tem .
j ust as with rising tem peratur e more p otassium chloride goes int o
solution ap d with sinking tem perature more crystalli z es out O n
. .
farther c OOl in g more and more ice wil l be de posited until in this ,
therefore c omplete .
, ,
we have the hydrous salt as the solid phase ; ab ove this temp erature
the anhydrous s al t This change must necessarily involve a sudden
.
N a zSO 4 I n sodium sul phate the Special case a ppears where the sol
.
hence the solubili t y curve falls as the temp erature rises above
I n the light of the ab ove the solubil ity of a substanc e which
has a transition p oint is the same for b oth mod ification s at this
p oint .This m u st always be the case ; it can be demon s trated in the
become equal at the transition p oint I ndeed the same figure can .
than that of the salt with m mols no matter what the form of .
,
b e tween the sal t and the water From the cryohydric p oin t .
u pward every bend in the solubility curve shows that a salt with
a d ifferent amount of water of crystalliz ation has been formed .
.
, ,
o r melt i ng p oint curve is then esp ecially valuable for the d isc ove ry
-
alone sep arates out of the fused mass on free z ing A t E however .
, ,
fused mass .
FI G 55 . .
FI G 5 6
. .
its meltin g—p oint When a certain amount of B has been added
.
now sep arates out of the fused mass The c ont inued additio n .
lowers the melting p oint of the p ure c omp ound The further
“
-
.
m
u te ct ic p i t is mo r g r l th n o h ydric p i t cry
Th e t e r e
“
o n t he e en e a a o n ,
“
l atte r t rm b i g u u ally trict d t qu us s luti
e e n
a s imil
E ut c t ic mix
re s
ly rel ate d ”
e o a eo o
re
on s .
ar
e
.
I N O R GA N I C C HEM I S TR Y 23 7
3 44 .
out and thereafter the melting p oint again rises along E QB t ill
,
-
—
dr at es which are indicated by the melting p oint c urve ( Fig
,
.
FI G . 57 .
of the above c omp osition The further addition of sul phur tri
.
z a t io n of this salt .
Sodium sul phate is only one of a large number of salts cap able
o f forming solutions of this nature Sodium thiosulphate and many
.
called su pers atu rated They are perfectly stable ; neither rubbing
.
with a glass rod nor Shaking (which trea t ment ordinarily tends
to induce crystalli z ation) causes the formation of c rys t al s prov ided ,
\
no trace of the solid salt comes in contact with the solution Such .
, ,
N 3 2 8 0 4 1 0H2 0 .
The sm allest am ount of salt (crystal nuc leus) that is suffi cie nt to
d i st urb and thus c ause the di sappearan c e of a m etastab le syste m such ,
nature of the solute the temperature of the solution and its con
,
srum sodium and the alkaline earth metals are almost com pletely
,
s alts ; those o f the al k al ies are practically com pletely ioniz ed whil e ,
FI G . 59 .
, ,
~
c onta c t .
2 39 . the solution
In of an extensively ionized salt we should
ex pect to find the pro perties of the cation and the anion I t must .
exhibit the sum of the pro perties of the two ions or to use other , ,
salts of the same metal all give the same reactions ; from the solutions
of all lead salts for instance hydrogen sul phide preci pitates black
, ,
the solutions of salts of the same acid are all cha racterized by the
s ame reactions ; sul phates for exam ple by the p reci pitate they give
, ,
when we recall that the solid salts are markedly different from
e ach other in their p ro perties but we are forced to j ust such a con
,
’
the anion Mn 0 4 in the co pper solutions the cation C u
, which ,
When the so lvent i s one i n whic h i oniz at i on does not occur the ,
so lu t i ons of cu pric chl ori de and nitrate ; t h e form er i s dar k green the ,
,
3 50 I N O R GA N I C C HE M I S TR Y . 23 9
mole are mixed the same caloric e ffect will be observed This
, ,
.
when two dilute salt solutions are mixed there is no caloric e ffect ,
AC I DIM ETR Y A N D AL KA L I M ET R Y . TH E O R Y OF
I N DI CA T O R S .
Slowly added from a burette When the point has been found at .
E xamp l e . Determi ne t h e
am o unt of nitri c a c id present in a li ter of a
so lu t i on of thi s a ci d i f 1 0 cc are ne utraliz ed by . cc of a norm al alkal i .
a hundred t imes as m u ch or g , .
f .
basis for all of these are crystallized solids and can be easily obtained
,
—
etc gram equivalent of sodium hydroxide or potassium hydroxide
.
,
p l ate w i th a ho l e i n i t thro u gh wh
,
ic h the no zzl e of a b urette i s passed .
'
less in acid solutions ) m ethyl ora nge ( yellow in alkaline red in acid
, ,
alkaline acid
SO 1u ti on to an solution in the presence of one of
acid alkaline
3 52 I N O R GA N I C C HE M I S TR Y . 2 4 04
241 From the stand point of the ionic theory the following
.
existence the alkali com pound of the latter being strongly diss o
,
due to this di fference in color of the non ionized molecule and the -
anion O n the other hand if the acid is a weak one there w ill n o t
.
, ,
—
is com pleted in other words the cha nge of col or bec om es m or e
, ,
that case n ear the end of the titration the solution will o nly contain
carbonic acid which is very weak ; consequently the color change
,
the acid itself and whose alkali salts are sufficiently ionized t o
produce a distinct change of color A very suitable one for this
.
reasons set forth above O n the other han d in case a weak bas e
.
, .
54 IN O R G A N I C C HE M I S TR Y . g§ § 242 .
p rocess is re p eated until all the iron is eliminat ed The resul ting .
2C u 2 0 (3q 6 0u S0 2 .
Fin ally it is fus e d with c oal to reduce any c o ppe r oxi d e remainin g .
“
ti es re mai n i n so lut i on or are depos ited as powder Fro m thi s powder .
conn e c ted with the pos i t ive po l e and the thi n Sheets with the negat ive
po le of the dynam o current pur e c o pper i s depos i ted on the Sheets
, ,
wh ile an e qui valent am ount of the crude copper disso lves to take i ts
p ace
l .
r ather hard but very extensible and flexible ; it can be drawn out
into very fine wire and beaten into extremely thin Sheets imitation
(
gold leaf) which are green in trans m itted light Sp
-
, . .
, .
o ther metals .
C O M PO UN DS O F C O PPER .
For b r o n z e s see § 1 99 .
p laster cast in c om p act form so that all the detail s of the original
,
C o m po u n ds of C o ppe r .
2 43 . C oppe r
forms two sets of salts which are d erive d from t h e ,
C UPR O US C O M PO UN D S .
C u pr o u s
o xi de , C u g O can be obtained from cupric salts in
,
7 60
of the oxygen of the a 1 r 1s -
1 52 mm . C u prous ox i de di S
5
solves in ammonia ; this solution ra p idly turns blue because of
the absorption of oxygen the cu prous oxide going over into ,
C l lz o HQ SO 4 C U SO 4 + O H Hg O .
3 56 IN O R G A N I C C HE M I S TR Y . 243 ,
Of the c u pro u s s alts the Sul phate and halides are known .
e rt y in gas analysis .
liberated
2Cu S0 4 + 4 KI = 2 K2 80 4 + C u2 1 2 + 1 2 .
C UPR I C C O M PO UN D S .
2 44 . C u pri c
o xide , C u O is a dense black p owde r o b taine d b y
, , ,
o rga ni c a nalysis .
~
, ,
formed .
ence can be attributed to the breaking u p of the salt into its ions ,
for all dilute C o pper solutions are blue no matter what the acid ,
2 0 1 00 parts Hg O dissolve
°
C oppe r nit a e , r t
can c rystallize with three or Six
C u (N 0 3 ) 2 ,
molecules of water an d is dark blue .
C o ppe r c arb o n ate The normal salt is unk nown but b as ic salts
.
,
a
p p er etc
,
1 5 7 )
. is being restricted .
hydrogen sulphid e .
SI LVER .
troy ounces kg ) .
by blowing air into the solution and thereby oxidizing the sodium
,
the silver all goes into the lead and is recovered from it in the
‘
following way : The argent iferous lead is fused and then c ooled
Sl owly till it begins to c ongeal Jus t as pur e ice crystallizes out of
.
a d ilute salt solution on cooling so the lead sep arates out her e ,
in crystals free from Silver These are removed and this process
.
—
c alled Pa t tin on i i g after its inventor
s z n is ke pt u p til l the percent
age o f sil ver reaches about Th is rich lead is then subj ected
to the 0 u p e l l a t i o n process i e the lead is fused in a rever
,
. .
by the p orous material ( bone ash or clay and limes t one) o f the
-
’
A nother method ( PAR K E S ) involves the princi ple of dis t ri
b u t io n between two slightly miscible solvents ( O R G C HE M . .
,
metal hard er .
Th e m arket pric e of Silver o n a gol d bas is was alm ost c onstant fro m
, ,
, .
be ing in 1 9 1 1
C o m po u n ds of Sil v e r .
p reci pitate when the solution of a Silver salt is treate d with caustic
—
s oda or baryta water free from carbo ni c aci d It is somewhat sol .
bon dioxide from the air and the Silver salts react neutral while t h e ,
°
heati n g to 2 50 Silver oxide 1 s broken u p into its elements It is .
o
,
” “
t i on with hydrochlori c aci d or a soluble chlorid e like so dium chl o
ri d e ; it fo rms a characte ristic cur dy precipitate I t is al most .
c onta ins no other s ilver sa l t nor any other c hl or i de I n View of the very
.
chl ori ne ions are now introdu ced into the liqui d the ioniz at i on of the ,
them .
Silve r chlo rid e dissolves readily in ammo nia potass ium cyani de ,
—
If a solution of Sil ver chlorid e an d ammo n ia is allow ed t o evap _
o rate in the d ark at room tem perature S ilve r chlo ri d e c rys t alli zes
,
on co o ling form a horny mass whi ch can be cut with the knife
,
horn Silver cf
-
,
. Sil v e r fl u o ri de , A gF is much more solu ,
"
,
- 2 KO N + Ag .
64 I N O R GA N I C C HE M I S TR Y .
M 246
if the ano d e is of platinum cyanogen gas is set free from the anion
,
All the S ilver salts p ar ticularly the chloride bromide and iodide
, , ,
c ial l y by the violet and ultra violet rays of the Sp ectrum ; as a result
-
the halogen p asses off and the c olor of the salt becomes fir st viole t
an d then b lack A b lackened pre paration of this sor t c an be re
.
“
d i pping the plates so pre pared into a solution of s ilver nitrate ,
“
t h e Silver halide was formed on them These were the wet .
”
p lates :
n o w they are almost entirely su erseded by the
p dry
p lates.
t here
“
apparatus which is essentially a cam era O bscu ra and the plate is
,
,
,
having co llected to form l arger o nes wh ic h render the m ass o pa que and
,
therefore inc rease i ts absorpt ive power Th e ripened s ilv er bromide gel a .
mixt ure of s ilver bro mide with s o m e ul tra mic ros c opic particles of Silver -
.
When A gBr i s e xposed to the li ght ordinarily ( apart fro m ge lati ne) free ,
estab li shed
—’
A gBr< A g Br,
which is displ aced farther to the ri ght the stronger the il lum ination , .
Li ght thus plays the sam e ro le in thi s di ssoc i ati on as heat in other di s
so ci at i ons If a gelat i ne pl ate i s used the latent i m age re m a i ns for
.
3 Deve l oping
.
— This process is e x plained by so m e as fo ll ows : By
t he reduci ng a c t i on of the deve l o per Silver is i m m ed i ate l y s e t free fro m
silver s ubbro mi de b u t not fro m Silver bro m ide notwi thstandi ng that ,
the l atter is c apable o f be ing reduced The syste m Silver bro mi de plus
.
m o l ecul es tak es place only upon those m o lec ul es already there and
not on spots where there was no subbro mi de originally i e Silver is ,
. .
depos i ted onl y where the li ght acted on the plate A c cord ing to this .
water .
p
ar t a t room
temperatur e) and melts at
“
I n medicine it is frequently
employed es pecially as a caustic ; it goes under the n ame of lunar
,
”
caustic I ndelible i nk s are also pre pared from it
.
.
G O LD . 3 67
Si l v e r
itrite , A gN O z is formed as a yellowish preci pitate on
n ,
mixing an aqu e ous alkali nitrite solution and silver n itrite ; it dis
solves in b oiling water and c rystalliz es on c ooling in beaut iful
needles .
G O LD .
,
.
reefs are se l do m m ore than one m eter thi ck b u t e x tend for miles east and ,
west ; the i r de pth is unkno wn They are mi ned by bl ast ing with dyna
.
mite ; the l arge pieces are reduced to about the s iz e of an egg in a heavy
iron apparatus and then sent to the stam ps that move in a l arge trough ,
the fine a uriferous slim e whi c h is m ade to fl ow over am algam ated copper
,
By thi s process the ta ili ngs are a ll owed to stand for fro m one day to
three w ee k s i n contact wi th a to p otass ium c yan i de so lu t i on .
2A u + 4 K C N 2HzO =
O z 2KA U( C N ) 2 + 2K O H HZO z .
Fro mthis
o l ut i on t h e g ol d i s obta i ned by e l o c t r ol y sis between stee l
s
anodes and l ead c athodes A t the anode Pru ssi an blue 3 08) i s form ed .
,
[Part icul arl y in the Un i ted States two pro c esses ( ch l or i nat i on and
cyani de) are in general u se for e x tra c t ing g ol d fro m its ores wi tho u t
am al gamati on B oth pro c esses are espe ci ally applic able to l o w grade
.
-
and s ul phuro u s ores e g the te lluri des of C o lorado I n the chl or in ation
,
. . .
after which the gol d i s pre ci pi tated wi th hydrogen s ul phide and roasted .
Th e cyanide pr oces s i s muc h Similar to that des c r i bed above for treat i ng
the tailings bu t zi nc generally serv es as the pre ci pitant i nstead of e lec
,
t ro l ys is .
very soft ( much like lead ) and extremely malleable and ductile
, .
. .
C em ica l Pr operties
h —
G old is the typical re presentative of t h e
precious m etals ; it is not attacked by acids and is dissolved only
by chlorine water aqua regia and potassium cyanide solution (see
-
for industrial p ur p oses For these purposes the pure m etal is too .
.
3 70 IN O R G A N I C C H E M I S TR Y .
M 2 5o
r o
Au u s io i
d de is fo rmed ( like cu pr ous io did e ) o n t r eat i ng a
known .
A u ri c C o m po u n ds .
A u ric c hl o
,
ri de can be obtained
Au C l3 , b y d issol v ing g ol d in
wh ich can be regarded as chl or—au ric acid M any salts of this aci d .
s alts give the ordinary tests for gold hence this acid eithe r fo r ms ,
chloride with magnesia The latter can be r emoved from the pre .
c ipit at e with concentrated nitric acid the auric oxide remai n ing ,
obtained which dis plays acid instead of b asic pro pe rties Salts
, , , .
p ound A u ( O H ) 3
— H2 0 = Au O O H P otassium aurate for exam -
.
,
p l e
,
has the formula K A q l 3 H 2 0 and crystallizes in yellow - -
needles M any other salts are also k nown ; the above mentioned
.
-
preci pitate with magnesia for exam ple can be looked u pon as t h e , ,
an d acetylene water serve very well for this pur p ose Hyd r oge n .
kl
peroxide preci pitates gold q u y in alka l ine solutio n
ig .
fro m the baser m etals I t i s needless t o say that the i r efforts were ne ver
.
e x tent of our m astery o ver natural for c es the i m poss ib ili ty of de com ,
p os i ng g Ol d or synthesi z ing
~
it from other e l e m ents 1S by no m eans ab so
l u t e l y estab l ished ( Se e 2 66 .
lim ited knowledge that the pro pert i es of the m etal s c oul d vary N one
, .
, .
The m etal s thus obta i ned had no de fini te pro pert i es ; distinction was
m ade between various sorts of l ead co pper etc The m utab ili ty of , , .
the m etal s m ay be said to have been the fi rst princ i pl e w h ich observation
taught ; indeed when a pie c e of m etal is fused with sm all am o unts of
,
Moreov er at the t ime of the a lc he mi sts the present conce pt e lem ent
,
,
.
“ .
, ,
de prive the baser m etal s of c ertain pro pert i es and substitute others ,As .
to the m etals the m se lves the idea was prevalent in alchem istic cir cles
that m er cury was the pri m ordial substance and that it h ad u ndergone
vari o u s changes Before go l d c ould be m ade fro m it it m ust be m ade
.
“
depended on t h e co Ope r
,
SUMM A R Y O F THE G R O UP .
2 52 . Th e
metals C o pper Silver and gold form a b ri d ge from ,
10 5 19 3 3
‘
8 94
.
.
1 08 3 961 1 06 3
re d wh eit re d
l arit y in the pro per t ies of the higher s t ages of oxi d a ti o n This is .
BE R YLL I UM AN D M A G N E SI UM .
I . Be rylli um ( G lucinum ) .
2 53
This
.
is one of the rarer e l e m ents I t o cc urs in the mi neral beryl
.
,
A l 3 that v ar iety of beryl whi ch i s co l ored green
by traces of a c hro mi um c o m pound i s the gem ca ll ed em erald or s m aragd , .
m
the a lu i ni um i s then re m o ved by crysta lliz ati on i n the form of al u m ,
3 74 IN O R GA N I C C HEM I S TR Y .
m 2 54.
II . M agn esiu m .
m eerscha u m H4 Mn i3 0 1 0
,
I t is found in smaller amounts in .
many other silicates e g horn bl ende (as bestos) augite tou rm alin e
,
. .
, , .
O ther sal t s foun d in nature are carna ll ite MgC l z KC l 6H2 0 kic ,
- -
s crite,
MgSO 4 Hg O and kain ite MgSO 4 KC l 3 HzO (Stassfu rt
-
, ,
- -
turns red litmus b lue ; however in an excess of alkali its ioniz ati o n
is so diminished that it becomes practically insoluble It is a .
, , ,
N H3 + HQ O (cf As a result
. of this reaction O H —ions dis “
a ppe ar In order to restore the equilibrium between the undis
.
this process will go on till all the magnesium hydroxide has entere d
into solution I t now becomes clear why on the other hand the
.
, ,
M A G N E SI UM SAL T S .
OH
On eva p orating the aqueous solution the basic chloride M g
Cl
,
and hydro chloric acid are formed ; sea water cannot be used in -
chloric acid set free attacks the iron M any double salts of mag .
,
-
red heat .
i h t
M agn e s um sul p a e , MgSO 4 7 2 H 0 E ps om s a l t fin ds us e in -
, ,
further analogy between these sul phates a ppears in the fact that
with sul phate of potassium or ammonium they form double salts of
the same type K zSO 4 M gSO 4 6 H2 0 which are also isomo rphous
,
- -
,
.
I . C al c i u m .
2 56
This element is one of the ten princi pal constituents of
.
’
the earth s crust Particularly the o a r b o n a t e is found
'
calcium phos phate phosphorite apatite etc part icu l arl v in Spain
, , , .
,
.
y hydrogen flame
ox it-
emits an
intense white light I t absorbs water and carbon dioxide
from the air ; as a result the chunks of lime which are hard and ,
solid when they come from the kil n gradually crumble to fine ,
p owder .
ci
C al u m hy d roxi de ,
C a ( O H ) 2 ( Slake d lime ) i
,
s obta i ned by
slaking quick lime with water I t s formation is attended by
-
.
( forming l im e w a t er ) but
-
more soluble
,
in c old water than in wa rm .
stones A fter some time the m ass bec omes as hard as stone ; this
.
t he older the wall the harder the mortar The formation of cal .
“
slake ; it is therefore less adapted t o masonry purp oses an d is
“
”
called p oor or lean in c ontrast with t he pure easily Slake d
, , ,
”
fat lime .
”
the R hine region such a mixture occurs as tu ffstone which
, ,
with water sets very firmly in a short time ; this is due in all ,
C al ci u m pe roxi de , C aO z 8HQ O ,
is de p osited when lime water - -
on heating .
SALT S O F C A L C I UM .
u se d t o dr y t h is gas
‘
mix t u res are known ; the on e m ost fre qu entl y used i s that of c omm on
sal t and ic e wi th whic h a te m perat ure of 2 1 c an b e obtai ned I ce
,
— °
.
p rod uc ed .
l ibrium at for the sal t so lu t i on has a free zing po i nt muc h l ower than -
poss i b le as the ic e m el ts by whic h pro c ess heat i s c han ged i nto the ,
C h l o ri de
of lim e is a name given to a product o b taine d b y
saturating Slaked lime with chlorine at ordinary temperatures .
O Cl
however much evidence in favor of the formula Ca < accord
,
Cl
ing to which it is a mixed salt of hydrochloric and hypochlo rous
acids A t any rate this is more probable than the su pposition
.
ble in alcohol and almost all the chlor ine is ex pelled by a current
,
of carbon dioxide .
O Cl
Ca + 2 HC l C aC 12 E go + Cl2 ;
Cl
05
8? H
+ 2 8 0 4
= C aSO 4 + 11 2 0 + 012 .
as a c atalyz er .
'
tem perat ure Moreo ver t h e greater solub ili ty of the hal f hydrate as
.
-
4
-
,,
the air and dissolves rea dily in alcohol I t is converted into s alt .
ca me ) ,
2H28 0 4 2CaSO 4 .
, ,
c alcium sulphate that i s formed takes u p the water c ontai ned i n the
chamber a ci d to form crystal s .
”
so lubl e However t h e pho s phate i s now di ff u s ed w i de l y i n the so il
.
2 59 . C al c i um ca rb o n ate
is dimorphous o ccurring , C aCO g , ,
,
S A L TS O F C A L C I UM . 3 83
with soa p ; the fatty acids of the soa p form white insoluble salts
with the lime so that water containing much lime is not g ood
,
p osition into lime and carbon dioxide can only occur therefore , ,
GLASS .
and easily fusible The calcium silicates however are ins oluble
.
, , ,
are ve ry many diffe rent so rts in use Some of the mos t im port ant .
“
Besides the substances mentioned many othe rs a r e use d in gl ass
factories to im part particular pro perties to the glass Th e addi .
, ,
6 IN O R GAN I C C H E M I S TR Y 26 0
fro m liquids .
gold solidifies the com p onents do not se p arate but solid ify
, ,
II . Stront i u m .
to those of c alciu m .
carbonate The tem perature required for the com plete disso cia
.
tion of the latter is higher than that for the corresp onding calcium
com pound The hydroxi de Sr ( O H) 2 8 H2 0 is more soluble in
.
,
-
II I . B a ri u m .
re
p p aring the other barium sal t s it is merely necessary to dissolve
the latter mineral in the pro per aci d B ari t e howeve r mus t firs t .
, ,
( )
2
wa ter .
a cid
,
barium s ul phate is preci pi t ated and hydrogen peroxide left
in solution I f baryta—water is again a d ded t he h ydrate B aO z 8H20
.
,
c ryst al li z es out .
a nhydro u s
.
3 88 I N O R G A N I C C HE M I S TR Y . 262
a r i u m c ar b o n at e
”
t h e name of p ermanent white or bl a n c fixe B ,
.
SUM M A R Y O F T HE G R O UP O F T HE A LK A L I N E E A R T HS .
0 0 0 0 0 0 0 0
O O O O O O O O O O O O O O O O
"
I n res pect to the chemical pro per t ies it has already b ee n ,
remarked that these elements act only as bivalen t ; all com pound s
of the group therefore have the same formula type In the solu .
closely related in their pro perties while the two other members of ,
the group are unlike them in many res pects B eryllium displays .
s atisfactory for some ele m ents e g those of the alkali and alkaline
,
. .
latter s pectra are their greater light intensity the greater con ,
be co n tinu ed at length .
2 64
. The s pectrosc o pe is one of the mos t d elicate means we
have of detecting many substances This is readily seen on c on .
FI G . 63
found o n photogra phing s pectra that there are still more lines
in the infra re d and ultra violet p ortions which are invisible
- -
, ,
s pe c t iv el y
,
the s pectrum of barium contains 1 6 3 lines and that .
the green line of thallium and the blue lines of indium For .
ur
p p oses of identification of such elements these p rominen t lines
are generally observed directly i n the s p ectral a ppara t us .
'
Thanks to the researches of R O W L AND M I C H E L S O N K A YS ER , ,
m 4
constant ex presses the wave lengths A of the lines
of the s pectrum of the element with very close a pproximation ,
and it has been found that the regularities are in all of the cases
more c om plex than for the hydrogen s pectrum I t would lea d .
Sp ectral lines of one and the same substanc e o n the one hand ,
light from the latter is passe d through a p rism line s p ectra are ,
We ar e l e d t o p re s e th at um an y o f t h e m l m en ts to w h ich th e se l in e s
e e
are ill l
du e w v l
a s o b e r e e a e d on t h e e art h b
y m o e c are ful re se rch e p ci lly
r a , s e a
wh w
en c o id w h t a sm ll p t f t h
e ns er rt h i k n own ( s fo otn ot
a a ar o e ea s ee e,
o
h li m
e u Th p i n ci p l li n f t h e l tte D — r
te rm e d b c au of
a e o a e r, so e se
a
it s p ximity t t h d ou b l D—l i
ro o
( D D ) f e d ium — w
a b
e v d in t h e
ne 1 2 o so s o ser e
s pe c t f m n y fix d t
ra o s w ll
a in t h t f t h s n b f re t h
e s a rs a l m nt e as a o e u e o e e e e
i t l f w i d t ifi d
se as th rt h H lium w s th u di sc ov red in t h t rs
en e on e ea . e a s e e s a
b f e o re it w f u d n t h as th oIt in triki g f c t th t i t o ccur in
o e e ar . s a s n a a s
e xc di gly l g qu titi in t h fix d t
ee n ar e
(an
a cc d i g to
es
p
c tr m e
tr ic e e s ars or n s e o
o b v ti ) w h il t h is pp ntly ly a v y sm all m ount f it o n t h
se r a on s e e re a a re on er a o e
ea rt h .
THE UN I T Y O F M A T TE R
~
2 66 . .
3 95
, ,
,
t u al l y b een t h e c ase .
is not the e ntire ato m but smaller p a ti cles o f whi ch the atoms r
s pectral lines .
The physi cal i nvestigati ons of the last decade have furnishe d
subst anti al reasons for believing that th e chemi cal ato ms are no t
i n re ality the ultimat e particles of matter but that th ey are divi
sible i n to p articles ap proximately 2000 times smalle r than t h e
hydro ge n atom These p articles carrying with them as they do
.
tions of radi o active elem e nts C ath ode rays are generated when
-
.
The cati ons are formed from the ato ms b y t h e release o f one o r
more ele ctro ns We may thus write .
C l + d= C l '
an d K
the condu ctivity o f a layer of air that was ex p osed t o the rays .
radio active ele ments woul d h ave been imp ossible becaus e they
-
r adium chloride .
one that has been isolated and whose com p ounds have been
p pre ared in the p ure state I t s s p ark s p ectrum
. has three very
bright lines in the blue and violet and accordingly the B unsen
flame color is carmine I n its chemical behavior it shows close
.
being more diffi cu l t l y soluble than the corres p onding b arium salt
(this is true for all the res pective salts of the two elements ) .
cath ode and obtained a radium amalgam from whic h the mer
, ,
sto p them ; they form only a small p art of the total radiation .
[
ii
-
rays are to be regarded as cathode rays of great velo city .
—
enormous velo city ex plains the great penetrating p ower of fl rays .
FI G . 64.
— E FFE C T or A M A G NE T IC FI E L D ON T HE a
fi AND r
-
RA YS .
G O L D ST E I N
They behave as positively charged proj ectiles
.
the mass of the proj ectiles formed by the fl rays and the cathode -
These pro ceed from a metal plate which is placed in the p ath of
c athode rays ; they do not consist of a stream of electrically
charged p a rticles but are regarded as a form of wave motion of
,
the ether which originates when electrons are p roj ected with
,
cent .
well known vi z h e li u m
,
. R AM SA Y and SO DD Y have demon
,
. - 4
The law governing the rise and decay of radio active sub -
, ,
ic all y ; for u p on plotting the time on the abscissa axis and the
lo garithm of the activity on the ordinate axis the phenomenon
would be re presented by a straight line B u t when the subst anc e .
line but a rather com plic ated curve N evertheless it has been
,
.
,
This is not the only method O f asce rt aining the number and kind
of the intermediate p ro ducts We can often distinguish the
.
co oling .
we take
we have the case where the intensity of the r adiation has decrease d
to j ust half Solving for t we have
.
,
“
K K
being established .
the radium in the earth would long since have disa ppeared if ,
p ower their
,
effective limit in the air being less than 3 cm The .
ro
p p erty of ionium is that it can p roduce radium .
— V arious chemical
C hem ical Ej ects of R a di oacti ve S u bs tan ces
'
radium .
and the alkali salts ; the same color can be p roduced by c athode
r ays The skin is also attacked by these rays
. .
O ccu rr e R i S b —
n ce of a d oac ti ve u s t a n ces This is by no means .
.
,
elements but that all of them suffer decay even though in most
, ,
this is by no means proven but there are two reasons for such
,
Z IN C . 4 07
tellurium the platinum metals ; the rare earths The two last
, .
Z IN C .
( H 2 Zn 2 SiO 5 ) s m i th s
,
o n i t e o r bl en de ( Zn S) and ,
o r e s are roaste d — the gas (S0 2 ) from the sul phide o res is co n
—
verte d into sul phu ric aci d yiel ding z inc o xide I n th e ol der .
“
the receiver t ogether with a fine gray p owder zin c du s t This
”
dust is a mixture of zinc oxide and zinc p owder and is
, .
t ime the s pecific gravity rises to 7 2 and the metal becomes firmer . .
law is,
the molecule in the vaporous state can c ontain only
an d
0 n e atom The same is true of the related metals cadmium
.
'
water When heated to boiling in the air the metal burns t e zino
.
o ,
latinum wir e effervesce nce begi ns at once not from the surfac e ,
p ,
FI G 6 5. . FI G 6 6 .
of the z in c however but f rom that of the wire and zinc goes into
, , ,
Zn + 2 H
"
Zn + 2 H
°
cations into the solu t ion with great force itse l f thus assuming a ,
difference is not real Since in the case of the lead tree the fresh
,
tion of lead nitrate ( Fig 66) lead crystals are de posi t ed n o t on the
.
41 0 I N O R G A N I C C HEM I S TR Y . 27 0
C ADM IUM .
2 70 . C a dmium
is very frequently found in zinc ores Being .
dil ute nitric acid The cadmium molec u le in the gaseous stat e
.
MER C UR Y ( Q ui ck s il v e r) .
p i p es
, called a l u del s I t I S b r ought on t he market In 7 5 l b iro n
.
-
.
flasks .
M E R C UR Y . 41 1
dete c ted by the fact that they m a k e t h e m erc ury adh ere to a gl ass v essel .
FI G . 67 — PUR IFIC AT I O N
'
OF M E R C UR Y .
Physica l Pr op er ties .
-
M ercury solidifies at
and boils
at E ven at ordin ary tem p eratures it is somewhat volatile ,
es pecially under redu ced pressure ; when gold l eaf is sus pended in
a bottle over mercury for instance it eventually becomes white
, , .
4 12 I N O R GA N I C C H E M IS TR Y 27 1
3
, .
.
s ilver amalgam can thus be pre p ared Some metals such as tin .
, ,
in g e n e r al a re mixtur e s o r c o mp o u n ds
, I n o r de r t o s o lve t h e q ue s t i o n a .
s tudy h as b e e n m ade o f t h e fr e e zi n g
p o i n t cur ve s ( of 2 3 7 ) o f d i ffere n t p a irs
-
.
—
FI G . 68 T .
YP IC A L FREE Z I N G P I NT
— O C UR VE S OF PA I R S or M E T A LS .
of mt l e a s .
l i f m ti n ft
A dd fit i d ci iv
on a tu e h b e e n
n or a o , o en o a e s e na r ,
as
a ff d d b y t h
or e e mic
c p ic l xami ati n f t h e u f c f t h all y ft r
ro s o a e n o o s r a e o e o a e
h vi g b e e n t c h d w ith d ilut
a n eci d d p li h d t h i divi dual c y t ls
e e a an o s e e n r s a
,
b e i g ge n
n
ll y di ti gui h ble i th i w y A a e ult f th e i v t ig
era ,
s n s a n s a . s r s o es n es a
t io n i t h as b e n f un d th at t h e f e zi g po i t curve fo pairs f m t l
s e o r e n -
n s r o e a s
b uttur ns d ark in t h e t
light on accoun of the se paration of metal «
2 Hg C l + 2 N H3 HZN Hg C l Hg + N H 4 C I .
p rod uc ts u n i te a ga i n on c oo li n g b u t they c an be
, pre v io u s l y se parate d
by di ffus i on I t i s for t h e abov e reason that the v apor dens i ty was fo und
.
to be half the am o unt c alculated for HgZClz ; hen c e the correct form ul a
of c alo m el is n Clz .
Me r cu ri c C o mpo un ds .
2 73 . M e r cu r i c
i de ,
E g O is red and c rystallize d when pre
ox ,
2, .
,
stan c e whose m od ific at i ons i nter c hange quickly on passing the tran
‘
crystals .
undi sso ci ated Hg Cl2 m o le cules are formed while the mixt ure of so lu ,
e xplai ns the reverse fact viz that the hal ogen c o m po unds of m er cury
, .
,
tate all the m er cury fro m m er curic chloride a l arge e xcess of potass ium
hydro xi de must b e e m pl oyed ; m er curi c iodi de an d m er cur i c c yani de
cannot be de c o m posed by potass ium hydro xi de al one Mer curic cyani de .
is so li ttle i oniz ed that i ts c onduc t ivi ty can hardly be m eas ured ; henc e .
it does not give any of t h e ordinary mer cury rea c t i ons e xc ept the forma ,
non i oniz at i on
-
.
Thi s l o w ioniz at i on also e xpla ins the form ation of m erc uri c c yani de
a cc ording to the method m ent i oned above Wh en m er c uric ions and .
cyanide i ons are bro u ght to gether even i n e xtremely dilu te so luti on
, ,
The m ercur i c hali des (espe c ially corros iv e subli m ate) are very strong
anti se pt ics I t i s an i nterest ing fa c t that in thi s respect also they
.
,
be c o m e m ore e ffe c t ive as the i r i oniz ati on i ncreases The chl ori de i s a .
chl ori des dimi ni shes t h e ioniz atio n of s ublimate and at the same t im e
reduces i ts dis i nfe c t ing ability .
The reason why t h e mer curic chlori de for u se in s ub lim ate tablets is
ne verthe less mixed wi th a n e xc ess of c o mmon sa lt i s part ly that the s ub
limate i s thus disso lved m ore rapi dly and also be c a use s uc h so lut i ons
keep l onger than those of the pure s ublimate es pe ci ally when prepared ,
w i th we ll water
-
.
mercuric oxide by boiling with water This shows that the bivalent .
yellow com po und HgSO 4 2 HgO is formed With the sul phates of
, , .
E L EC T R O C H E MI ST R Y .
2 76 As
early as the beginning of the nineteenth century when
.
,
“
numerous chemical phenomena The key to the explanation is
.
”
the conce pt of electrolytic solution ten sion which has already ,
This force c alled the e l ec trolyti c s ol u tio n t en sio n , c omes into action
,
u sual chemical means The cause of this is not tha t the solution
.
—
tension is low o n t h e c o n t r ary the latter is often very large
, ,
‘
p ossibilities to b e d istinguished :
( 1 ) P > p The metal then behaves like a sal t in c ontact
.
with its own unsaturated solution I t forces cations into the solu .
negative electrici t ies acq u ired by the el ectrolyte and the metal are
c onducted a w ay by a c onnecting wire the metal will again send
cations into the solution and this action will c on t inue t ill p reaches
,
the value of P .
( )
3 P < p In
. this case the metal c orres p onds to a sal t intro
du ce d into its supersaturated solution C ations are n o w de p osited .
P
“
( 1)
5
:
n
tudes are meas ured in other un its than those there em ployed In .
0 86 0 X 1 0
.
—4
X 2 3 02 5T
. log 5
P
n
1 log 5
1
2
E = 10 4
‘
-
.
.
n I7
F rom this equati on it is seen that E increases arithmeti cally when
p decreases ge omet rically For exam p le if the i oni
. c c oncentration ,
, E only increases by zx
g
volt . It is
n
420 I N O R GA N I C C HE M I S TR Y
be quite large .
in C o pper sul phate and zinc in zinc sul phate the two p airs sep arate d ,
P1
17
21
of the latter are v ery s m all i n c o m pari so n to the form er so that they ,
m ay be d is regarde d .
L eaving t h e s ol u t io n t e nsion s P1
of c onsideration an d P2 ou t ,
P3
l oge < log — E becomes n e g at 1 v e , 1 e the current m us t alte r
F
e , . .
1 9
22
it s direction This can be demonstrated as follows
.
ions (pl ) is seldom very di fferent from that of the c o pper ions
( pg) the curren t goes from the c opper through the c onnecting
,
wire to the zinc for the solution tension (P1 ) of the zinc is much
,
hydroxide nor the preci pitation by ammonium sul phide reduces the
concent ratio n o f the co pper ions enough to produce this e ffect .
and when 192 p l the last ex pression bec omes zero it is a arent
, ,
pp ,
with lead peroxide ( positive) and lead sul ph ate ( ne gat ive ) .
The positive plates are al l c onne cted with each other as are ,
the other the cathode plate the lead sulphate is c onverted int o
, ,
the discharge the p eroxide plate is again p ositive the lead plat e ,
fore expressed by
Ph O z Pb 2H280 414 > 2 Pb 80 4 2 H2 0 .
”
t iv e l y charged Pb O z ions Thereby it of c ourse imp arts to the
.
”
bivalent Pb O z ions encounter positively charged Pb ions at t h e
cathode plate which are being sent by it into the solution ; the
,
Ph O z "
cules which yield lead sulphate with t h e s ul phuric aci d presen t :
Pb 2 Pb O ; 2 Pb O 2H2 SO 4 2 Ph SO 4 + 2H20 .
action on the nitric or chromic aci d O n the other hand the zinc
.
p late sends p ositively charged z inc ions into the solution to the
same exten t as hydrogen ions d isappear the zinc plate itself ,
t he stannic ch l o n de an ac idu
lated sta nnous chloride solution : 1 00) is introduced into Zl
‘
4 I N O R G A N IC C HE M I S TR Y cr7u .
H
( g or
° °
.
, ,
will rise from the platinum plate of the other electrode kg and
the needle of the galvanosco pe will indicate the passage o f a power
ful current outward from kg The hydrogen of the palladium .
foil sends positive ions into the solution which however forth , , ,
accom plish this two tubes sealed at the t o p and fitted there with
,
are filled one with hydrogen and the other with chlorine (oxygen)
,
6 IN O R G A N I C C HE M I S TR Y . 27 7
fused into each cylinder and the two are c onnected by means of a
metallic wire O n t op of the mercury is some insoluble mercurous
.
the tem perature is raised still higher the solution in A will become ,
2 7 8 A s was remarked in
. 2 7 6 the electromotive fo c e which
,
r
. c an
tities of this equation are known with the exce ption of P which ,
ample :
The potential difference between magnesi um and the no rmal
solution mole pe r liter ) of its sul phate was determined to b e
volts The equatio n thus becomes
.
P
1 22 = 1 0 4
T log
‘
P
since fo r magnesium n = 2 p is the osmotic pressure of the Mg
.
ions O n the assum ption that the sal t is entirely Split u p into ions
.
,
p is A t m for
. osmotic p
,
ressure being equal to gas p ressure 1 ,
.
, ,
Therefore at 0 we have
,
°
X 2 7 3 (l o g P log 22
or log P whence we have a pproximately , ,
P 10
= 43
.
M e t al .
N ick e l
Hydro g en .
C o ppe r
M
di ffers in differen t substances For magnesium and zinc it is
.
com paratively large errors in the above data due to the difficulty ,
of deter mining the potential difference between the metal and its
s al t solution the o r d e r of the decimal ex p ressing the value of P
,
i l b m t l s a n d th eir
S om e of th e s e d iffe r e n ce s of p o te n t a e t w ee n e a
no r m a l s a l t s ol u t io n s are as follows :
M e t al .
tive in res pect to a co pper solution for even in the mos t dilute ,
goes into solution and the other remains intact A piece of gal .
e v e n in those places
-
p otassium hydroxide ,
for exam ple O,
H ions-
are liberated a t t h e
anode ( they are at once decom posed however into water and
, ,
”
Th e symbol O represents a secondary ionizatio n
p roduct of the hydroxyl ion
D I S S O CI A T I O N T EN S I O N S
.
E LE C TR O C HE M I S TR Y . 43 1
metal is deposited o n the other one the two metals form with t h e ,
Th e fo rmula
7 P
1
g
= 4 —
E 10 T
' '
-
'
log
n P
012 ZBI Bl g
' , ’
This is not su rprising in the light of the above consid e ratio ns for ,
the chlorine in order to enter the ionic condition mus t m ake use
, ,
’
Of the ion O of which there is only an extremely small amount
2 IN O R G A N I C C HE M I S TR Y . 281 g
much larger amount and whi ch after the loss of its negative
charge would also yield a quantity of oxygen equal to that of the
chlorine holds its charge more than
,
volt firmer than the
chlorine ion in acid solution .
2 2 3 226 242
,
2 4 8 and elsewhere )
, , ,
.
BO R O N .
element melts between 2 000 and but has such a high vapor
°
comp ound A1B 1 2 crystalli z es out B oron takes fire in fl uorine and .
—
r e d heat Heating with nitric and sul phuric acid converts it
.
(like aluminium
2B 2 KO H 2 H2 0 2 KB O z 3 H2 .
little with steam and when the c oncentration has bec ome grea t
enough it crys t allizes out I t is p urified by c onver t ing it int o .
The vo lat ility of bori c a c id with steam has for a long t im e been
re garded as an es pec i a ll y i nterest i ng pheno m enon be c a u se the an h y ,
o c curred ;
If H3 BO 3 m olec ul es vo l at il i z e wi th the water the con c entrations of ,
.
p or ,
ur
p p ose it is frequently used A t 1 00 b oric acid loses 1 molecule .
°
which is b orax .
meta bo ric aci d forms several They are un s t a b le and are c onve rt ed
.
Th e b es t known sal t
-
b oric acid is b o rax , N agB4 O 7 1 2 HQ O
of -
,
, ,
vitreous mass This glass has the pro perty o f dissolvin g met allic
.
e ver
,
a p reci pitate of g r ayish brown silver o xide is forme
-
d t h e ,
s olutio n .
AL UM IN I UM .
hydrate of aluminium and iron C lay and ka olin ( C hina clay ) are .
f p
elds a r m i
,
ca etc contain it,
as a base
.
,
A peculiar aluminiu m .
,
.
Th e art ifici al m anufa c t ure of rub ies and sapphires i s acco mpli shed
by fu s i g a m orpho u s l
n A w i
3
th l ead ox i de at br i ght red heat in a
H ess i an c ru ci b l e
. L ead a l um inate i s fi rst for m e d whereu p on the s
, ilica
of t h e c rucib l e causes t h e alumina to separate o ut in beau t iful c rystals ,
FI G 7 2 — PR E PARAT I O N
. . or AL U M I N I U M C H L O R I DE .
iC l3 PO C lg ,
°
etc have also been pre pared In organic chemist ry
.
, .
fi g so4 R 2 ( SO 4 ) 3 2 4H2 0 ,
’ .
The alums all cry stallize in octahedrons and cubes which oft e n ,
When two salts c omb ine we may have one of two results
either the new salt which is formed gives ions in dilute aqueous
O IN O R G A N I C C HE M I S TR Y . 2 85
solution that d i ffer from those of the two salts or it gives the same ,
alkali sil icate being dissolved out leaving the ins oluble aluminium
,
industries be ing used b oth for rough bricks an d the fines t china
,
ware ; of course the better grades requir e better sorts of clay Bricks .
“ ,
” “
are molded out of ferruginous and calcareous clays (loam ) an d then
baked ( burned or fir e d ) till they bec ome fi rm Un d er the .
head of ear then ware or porous ware (fa ience maj olica etc an d
, , , .
,
ar e com p letely filled with fused sil icate as a result of the addition ,
Ul tram arin e is a very beaut i ful blue pigm ent which is prepared arti ,
dilu te s ul phuric a c id and pre ci pitating with hydro c hloric (or better hydri
odic) a ci d where u pon the s par ingly solubl e chl ori de ( or iod i de) is
,
de pos i ted Thi s e le ment was a lso di s c o vered wi th the spe c tros c o pe
.
(C R o o x E s ); i ts s p e c tr um i s a br i ght g reen li ne .
lead Sp g
. .
m pt
.
,
.
I n m o i st a i r i t o xi d iz es v ery rapi dly
-
.
,
a d
n n i tr i c a ci ds d i sso lv e it read il y b u t hydro c h l or ic a ci,d a c ts very s l ow l y
be c au se of the s li g ht so lub ili ty of the c hl or i de .
fro m t h e o xi de l O a n d the t h a
,
ll i c c o m p o u nds fro m the o xi de T 12 0 3 ,
.
The form er resem ble those of t he a lka lies an d s ilver very muc h Thi s :
simil ari ty shows i tse lf for i nstan c e in the so lub ili ty of t h e hydro xi de
, ,
g iv e do u b l e sa l ts w i th p l at i n um c h l or i de e g l P t C l fi F u rther
,
. . .
p h a t e s ,
e g l .S O 4 . M g S O 4 6 H ZO~
wh ic h are -
ana l ogo,
u s to the c orre
s po n din g potass ium do ub l e sal ts O n the other hand thallium rese mb les
.
silver an d lead i n the sm all so lubili ty of its hali des (the iodi de i s t h e
least an d the chl ori de t h e m ost so lubl e) and al so in res pe c t to the
'
, ,
I n the thallic c o m po u nds the e le m ent is triv al ent lik e the other ,
SUMMA R Y O F THE G R O UP .
was observed with c o pper Silver and gold in the first grou p and ,
with zinc cadmium and mercury in the sec ond group The fol
, .
A to micw e ht ig
g vi
S e c ific ra ty .
e l ti n g p o i n t
-
THE R A R E E A R THS .
4 43
In
the spectra of G a I n and TI it is again noticeable that the
,
lines move towards the red end as the atomic weight increases
”
As
to their chemical nature it may be remarked that all the
elements of this group are trivalent and that the basicity of the ir
o xides increases with rising atomic weight ; boron hydroxide boric
(
acid ) has exclusively acid pro per t ies b u t the hydroxides of the ,
most of the lower oxides of the metals are more strongly basic than
the higher oxides it is not strang e that thallous hydroxide is a strong
,
b ase .
“ .
still much u n certa inty i n reg ard to som e of them part icul ar l y as to .
These e le m ents o ccur in vari o u s rare minera ls whic h have been fo und
princi pal ly in Sweden and G reenland viz cer ite gadolinite euxen ite , .
, , , ,
or thite , e t c .
I n order to i s o l ate t h e rare earths fro m the se mi neral s the l atter are
p owdered v ery fi ne l y a n d heated to fa i nt re d heat w i th c o n c entrated s ul
-
then tak en u p in ice water in w hic h they di sso lv e much m ore readily
-
higher tem perat ure) Fro m this co l d so lu tion they c an be pre c ipi tat e d
.
this gro up d i ffer m arkedly in the i r stab ili ty 0 11 heat ing ; hen c e another
m ethod of separat i on h as been devi sed by whic h t h e n i trates are de c om ,
i nso lub l e ne u tral c hro mates be ing depos i ted ) separat i ons c an b e ac c om ,
by abs orpti on bands thu s dys pros ium holmium and th uli um O thers
, , .
,
like yttr ium gado linium and ytterb ium whose o xi des a n d sal ts are ,
m any lines Furtherm ore in vest i gat i ons of t h e ul tra v i ol et spe c tra
.
,
yttrium erb ium e t c Y tterb i a (o xide) i s obtai ned by fra c ti onal heati ng
, ,
.
of t h e n i trate mix t u re (see abo ve ) Th e sal ts of ytterb ium are c ol orl ess
.
baran iu m (A d) an d cass iop eiu m ( O p) He fo und thei r ato mic wei ghts .
to be A d = 1 7 2 9 0 and C p = 1 7 4 2 3
. . .
heated in a current of n i trogen i t b u rns quant i tat ive ly to the n i tride TiN .
Titaniu m di o xi de T iO ,
o ccu rs as mineral in three m odific at i ons : r u til e
z, ,
, .
4
, . r
l izes w i th 9 H O Z .
Thor i a and cer i a are the essent i al c onst i t u ents of the in candes cen t
g as-
ligh t of A V O N W EL S.B A C H A fi nel y wo ven c otton m ant le i s
.
whi ch the two are conta i ned i n s uc h a pro port i on that after i gni t i on
the ash c ontai ns 9 8 99 % thori a and 2 1 % c er i a t e n th i s ashe n
— —
.
m ant l e e mi ts onl y a s m a ll pro port i on of red rays and rays of st ill greater
wave length b u t m a i nly g ives Ou t rays of shorter wav e length ; hen c e
-
,
-
or of the two o xi des i n a pro port i on di fferent fro m the abo v e produc es
Very l itt le li ght So far as the c eri a i s con c erned thi s i s d u e to i ts be i ng
.
gives l ess light than when not s m o ki ng That i t is not the thori a whic h .
, ,
the ir m ass i s s m all they are ab l e to rea c h t h e h i gh tem perat ure at whic h
,
they e mi t the des i red b rig ht li ght ; for t h e bri ghtness of a fl a m e in c reases
wi th abo u t t h e fifth power of t h e te m perat u re .
the thori um i s separated fro m the thorium X (by repeated pre cipi tat i on
wi th a mm on i a) t h e tho ri um is fo u nd to have ent i rely l ost i ts e m anat ing
,
p ower The
. thor ium X however h as strong e m anat in g p ower ; so we
, ,
cu rve ; o n t h e other hand t h e emanat i on gives rise s ucc ess ivel y to thori um
,
A B and C
, , .
g ro u p s the m eta llic c hara c ter be c o mes m ore p ro mi nent as the ato mi c
cent of vanadium The ore is roasted and fused wi th caust ic soda and
.
vanadate N H VO ,
separates out after a whil e as a sandy powder Heat
r s, .
vanadic a ci d .
C HR O M O US C O M PO UN D S .
is much more p ermanent in the air than the other chromium salts
and can therefore be used for their prep aration The h y droxi de
‘
C r (O H) 2 is yellow .
C HR O MI C C O M PO UN DS .
, ,
a red hot tube The amorphous com pound is green ; the crystals
-
.
substance C r 2 0 3 2 HzO
,
-
.
salts with weak acids such as c arbonic acid sul phurous aci d et c , ,
.
( f
o .
tion green deliquescent crystals of the com position cr2 016 1 2 H2 0 '
se parate out These crystals are also obtained from the solution
.
A — 1 3 00 the va po r
°
of the hydrogel in hydro chloric acid t 1 2 00 .
( nitrate chrome
,
alum has the p,
eculiar ro
p p erty of disso l v
slowly with the sul phate solution but ra pidly with other salts ) .
salt crystallizes out the sul pha te for instance w ith fifteen molecules
, , ,
viscid mass .
sul phate ) and that green chrom sul phuri c acids are formed “
H2 SO 4 from 2 mols
” -
. .
i e substances with a com plex chro msul phuric acid ion sinc e
,
-
. .
,
they do not give tests for either chromium or sul phuric aci d .
Thus only one third of the sul phuric acid can be preci pitate d from
-
solution are still present The transition from the Violet soluti on
.
2 C r2 ( SO 4 ) 3 + H2 0 H2 SO 4
v io l e t com pl ex io n
g re e n
p reci pitated .
4 52 I N O R G A N I C C HE M I S TR Y .
The chlori ne can then be com pletely preci pitated with silve r
nitrate at ordinary tem peratures I f the solution is boil ed fo r .
a time however and then cooled silver nitrate will pr eci pitate
, , ,
only two of the three chlorine atoms directly under the same con
dit io n s ; the third must have gone with chromium to form a com
p lex ion .
K2 C r2 0 7 H2 S0 4 3 80 2 K Q SO 4 C I 2 ( SO 4 ) 3 + H2 0
‘
.
C HR O MA TE S .
case the sul phuric acid itself H2 SO 4 is also a stable com pound
, , ,
, ,
all sul phuric acid do not deli q uesce in the air They are re adily
, .
Q C TO 3 C r2 0 3 30 .
C hromium
trioxide is a very powerful oxidizing agent ; its solu -
p otassium chloride .
fused potassium hydroxide absorbs oxygen from the air and forms
the peroxide thus becoming a much more active oxygen carr ie r
,
-
in sul phuric acid solution being itself reduced to chromic sul phate ;
,
c rz o ] '
4 HQ SO 4 K2 8 0 4 “i“ O rg (SO 4 ) 3 4 H2 0 30 .
the c athode porti on The liqui d o xi diz ed at the anode c an be u sed for
.
introduced i nto the c athode port i on while the liqui d whic h previ o u sly ,
When the current i s aga i n t urned on the liqui d at the c athode whic h , ,
at the begi nni ng of thi s se c ond o perat i on i s ric her i n s ul ph uric a ci d than
the liqui d a t t h e an ode yi e l ds i ts s urplus to the c athode liqui d I n thi s
, .
On heating potassium d i chro m ate wi th potass ium chl ori de and sul
h r ic a ci d a dar k r e d liqui d d i st il s over wh ic h has the c om pos i ti on
p u -
of c hro m ic a c id ; it is called c hr om yl l
c h oride , or chrom ium oxychl oride
KzC rzO 7 4KC I 3 H2SO 4 = 2 C r O zC l2 3 KZSO 4 3 HzO .
Cl
The se mi c hl or i de of c hro mi c a c i d
-
Cr O z < is known onl y in the
OH
,
form of sa lts The potass ium sal t for e xam pl e is obtai ned by heat i ng
.
, ,
Cl
KZC I 20 7 ‘
2 HC l 2 0r 0 2
OK
It crystalliz es in red pri s m s .
p er m anganate I n concentrated
. a qu eo u s so lu t i on de c o m pos i t i on s oon
occ urs the dichro m ate be i ng form ed and o xygen g iven o ff
, .
M olyb den um .
A very charact eristic t est for m olybdic a cid ( the most c ommon
molybdenum c om p ound ) is the followin g : the substance is m ixed
with zinc and sul phuric acid ; at first a blue c oloration ( a m olybdate
o f molybdic oxide ) a pp ears but it soon turns green and then brown .
TUN G STEN .
i t very sl owly b u t i t rapi dly disso lves in a mix t ure of hydro flu oric and
,
( K2U20 7 and N a2U20 7) are pre c ipitated whi c h are solubl e in a c ids ,
.
ing i n the ai r Uran ium sal ts are used to im par t to g lass a beauti ful
.
g reen i sh ye ll-
ow flu ores c en c e .
and by t h e redd i sh brown p re cipi tate w 1 t h potass ium ferro c yan ide For
-
.
SUMM AR Y O F THE G R O UP .
for exam ple all have the formula H2R 0 4 M oreover sul phur also
,
.
has the ability to form pol y ac ids (pyrosul phuric acid ) although it
is n o t so prominent as in the firs t named four elements Several -
.
o f their salts are isomor phous The strength of the acids d ecreases .
,
0 0 0 0 0 0 0 0 0 0
M AN G AN ESE .
3 This element
00 . is widely diffused in nature . Its most im
lustre Sp g = 7 2
. . . m . b . It under .
z SO 4 M SO 4 l 6H2 0
5H2 0 I t forms double salts such as K n — s imi - -
.
, ,
p o u s w t .
very unstable .
~
.
4 60 IN O R G A N I C C H E M I S TR Y . 3 00
whe reupo n air is fo r ced thr ough the warme d l iquid The manganous
'
Mn 012 2C aO O C aM n O 3 C aC lz .
3 When
01 manganese
. c om p ounds are fused with p otassium
hydroxide in the air or better in the presence of an oxidiz ing age nt
, ,
-
manganates display the sam e abso rp tion s pectrum viz five dark ,
.
,
2 K MII O 4 + 3 11 2 8 0 4 K Q SO 4 2M n SO 4 H "
3 2 0 i 50 ‘
Mn 2 0 7 ZMII O l"50
”
.
acid goes over into carbon dioxide an d water ; ni t rous acid in very
d ilute solutions is converted into nitric aci d from hydrogen
p eroxide water an d oxygen gas are forme d Al l these reactions .
tile bro wnish green o ily liqui d whose vapor e x pl odes easily yi elding
,
-
, , ,
acids are is omorphous and b oth are p owerful ox idiz ing agents -
IR O N .
rie d o u t in bl as t fu r n aces .
(fl u x see
,
according t o the grade of the ore I f the gangue .
,
The blast furnace previously warmed to the pro per tem pera
,
“ “
layers of c oke an d the mixture of ore and fl u x b o t h being intro
‘
,
”
du c e d in rounds / or charges 7
of definite weigh t ( Sometim e s
, .
7 3 ) are b uilt of fire brick encase d in iron and are o f much li gh ter
-
co nst ructi on than t hose formerly used They vary greatly i n size .
“
I n order to u tiliz e th e esca ping h o t gases (C O etc ) an a pparatus
”
( c u p and cone ) is fitte d o n the t o p to co ndu ct them o ff and
,
.
als o allo w th e intro duc tion o f the ch arge The air necessary for .
4 64 IN O R G A N I C C HE M I S T R Y 3 02
F8 2 0 3 3 00 2Fe 3 00 2 .
FIG . 73.
— B LAS T FURNA C E .
fuse but is extensible and malleable and the more s o the less t h e
, ,
to e xte n s ive inve st ig at io n s reg ardi n g i t n otw ith stan di n g that s uc h i n ve s tig a
,
o f c a rb o n in i ro n I t i s s o re g arde d b e c au s e m ic ro s 0 0 p ic s tu di es h av e sh own
.
3
. ,
w i th quick c oo lin g .
p in t
o in Fig
01 h ow eve r i t is n o t pure i ron b u t a s o li d s olut i on o f
.
, ,
92
FI G . 7 4 — I R 0 N 0 AR
.
-
B O N SYS TE M .
ca rb on in i ron th at r t ; it s c om p o s i t i on is sh ow n in t h e d i a gram
sepa a e s o u t
w e h av e s e p arati n g o u t at c , fo r e x am p l e t h e s o li d s u b st anc e w h o s e c om
, , ,
o f t h e cu rve A C w e c an fin d a p o i n t d d e t c t h at give s t h e c om p os it i o n
l, 2,
.
,
p o i n t is r e ac h e d A l o n g C B grap h i t e s e p a rat e s o u t ;
. a t C i t s e l f a mixtu r e
o f gr aphit e a n d m a r t e n s i te t h e c om p o s it i o n b e i n g give n b y D
,
Th e p o i n t .
C is at 1 1 3 0 an d o f c a rb o n Th e m a rt e n t it e form e d at th i s t e m
°
.
p e r a t u r e c o n t a i n s 2 % o f c arb on .
68 IN O R G A N I C C H E M I S TR Y .
s e p arat e out w e h av e a e ut e c t ic p o in t a t C
,
ve ry clos e t o C w h ere c e m en t ite
1, , ,
Fe 0 s e p arate s o u t w i th t h e m art e n s i te
3 , Fu rth er t h e lin e C E r e p re s e n ts
.
, , 1
A t E fe rrite is form e d to ge t h e r w i th c e m e n t i te
1
M arte n s i te c h an ges o ve r.
form s .
“
s o ft c o n gl o m e rate o f fe rri t e a n d c e m e nt ite ;
tem pe rin g o f st e e l ”
.
th i s is w h at take s plac e in t h e
acc ount sul phurous ores as such are unsuitable for the manu
3 5
0 From the
. crude i
pg iron the direct p roduc t of the blas t ,
furnace the other varieties of iron are pre pared For this purpose
,
.
470 I N O R GA N I C C H E M I S TR Y .
3 05 ,
FI G 7 6 . .
— HER O U LT FURNA C E .
c rucible process requi res The cradle sha ped H ER O U LT furn ace
.
-
res p ect to the iron carbon system (2) removing harmful o ccluded
-
solutions with iron Steel beco mes very hard and brittle for .
,
lined wi th i ron o re (o xide ) ; t h e c arb on and also t h e s ilic on are o xid ized
( an d so re m o ved ) part l y by t h e a c t i on of t h e a i r b u t m a inl y by that ,
i
p g
.
is obtained electrolytically an d by re du c
C hemical l y p u r e ir on
ing the oxide or chloride in a current of hydrogen I f the r e du c .
tion takes place at a low temp erature the resulting iron p owder is ,
kee ps on forming .
The rust ing of iron is greatly retarded by c ontac t with water c onta i n
ing a litt l e a lkal i or sal ts of alkal ine reaction I n a soda so l ut i on for .
,
water can be e x pla ined by assum ing that the oxygen dissolved in water
endeavors to for m hydroxyl i ons with the hydrogen ions I n order to .
c om pensate the ir negat ive potential the iron sends its positive i ons i nto
the so lu t i on ; i n a short ti m e the so l ubil ity product of ferri c hydro xi de
is rea c hed and the l atter is de posited ; in other words the iron rusts ,
.
water i s dim inished so m uch that the oxygen can find a lm ost no hydro
ge n i ons with whic h to for m hydro xyl ions ; therefore the iron does not
send any m ore ions 2 7 6 and 2 7 7 ) into the solution and rus ting i s
greatl y retarded .
results
3 Fe 4 H2 0 z Fe 3 O 4 4 11 2 .
In nitric acid (no t too c oncentrated ) iron dissolves rea d ily with
the evolution of nitric oxi d e N O but if the iron is firs t dippe d
, ,
I ron forms two sets of salts the ferr ou s and the ferric
,
.
I N O R G A N I C C H E M I S TR Y .
Ferric C o m po u n ds .
aque ous s olu t i o n most of the ferric salts even thos e o f strong ,
this it app ears tha t the ferric io n itself in aqueous solution is o nly
slightly c olored The ferric salts are readily c onverted in t o ferr o us
.
v arious iron com p ounds in the air and is manufac t ured by igni t ing
The re d dish brown colo r of the aqueous solution of ferric chl oride
-
m ust be asc ribed chiefly to u n ionized Fe 013 m olecules for the sal t
—
,
inc r eases on warming the dilute aqueous solution for a very dilute , ,
c olor .
2 4 H2 0 .
the ir on ions :
2 ( Fe
'
2 (H
‘
el f
) o 2 (Fe
' " Hg O
de Hy d d F de
.
Fe r r o u s c h l o ri r oc h l o ric ac i e rr ic c hl o ri
e x pla ined by su ppo sing tha t every ferr ic ion gives u p a third of its
Sal ts f i ron ao r e a l s o k nown whi c h are deriv ed fro m the hyp othet ic a l
08 unites I ron
with c y a n o g e n t o fo rm com p lex an d
3 .
.
,
iron sul phide ( animal refuse always contains sul phur c om poun ds) .
6 KO N Fe S K 4 Fe (C N ) 6 K 2 S;
2KC N + Fe Hz o Fe (O N ) 2 2KO H H2 ;
Fe (O N ) 2 4 KO N K 4 Fe ( C N ) R .
for the u n pu rifie d gas contains a little cyanogen and prussic acid .
FGC O 3 2 HO N fi Fe (C N ) 2 Hg O 00 2 ;
K200 3 2 HC N fi 2 KC N Hg O 00 2 .
c ipit a t e soon turns blue in the air on acc oun t of the formation of
of this acid have characteristic colors and are ins oluble ; hence
p otassium ferrocyanide finds use in analysis I t is an interesting
.
47 8 ,
I N O R GA N I C C HE M I S TR Y .
C O BAL TO US C O M P UN DS O .
,
. .,
c u pric chloride
c ate is very dee p blue ; hence its use for colori n g glass Pulverized .
alumina .
C O BAL TI C C O M PO UN D S .
L ike iron cobalt also forms com plex ions of which those with
, ,
cyanogen are very stable There are cobalt salts corres ponding in .
com position to the yellow and the red prussiates of potash ; the
sal t K3 00 ( 0 N ) 6 potassi u m c o b al t ic yan ide crystallizes in colorless
, ,
rh ombic prisms A pe c uliar com plex ion o c curs in the potassiu m
.
C O BA L T A N ) " N IC K E L . 47 9
c o b alti c nitrite , 6 KN O z or
n HzO It is form ed on t rea t i n g a solu tion of a c obalt sal t wi t h
.
p rese n t in excess in t h e li q ui d .
N i ckel .
“
3 1 1 o.c curs N ickel
in n ic c ol il c N iAs an d n ickel g l an ce o r , , ,
lytically .
air .
.
,
sal t s .
,
.
with hydroc h loric acid it yields chlorine gas and ni ckel c hloride .
4 80 IN O R G A N I C C HE M I S TR Y . 3 11
N i ck e l ,
ca rb o n yl
is formedN i( C O ) 4 ,
when carbon monoxide is
led over finely di v ided nickel at ordinary tem peratures A state .
Ni -
N i( 0 0 ) 4 ,
which is dis placed to the left with rising tem perature since t h e ,
S howed at the same time that both the formation and the de c o m
substances .
i
a d in extracting nickel fro m low —grade ores .
b
‘
3 1 2 A.
p e culiar ro
p p erty is exh ibited y t h e s u l ph i de s o f c o b al t
and nickel 0 0 S and N iS Hydrogen sul phide does not pr eci pitate
,
.
ammo n ium sul phide ) they are a pparently not redissolved by dilute
,
for th e sul phi de sh ould either be prec ipitate d by h ydrogen sul phid e
fro m a feebly acid solutio n (e g C u S) which is the case whe n t h e
. .
,
sul phid e As a matter of fact h owever no real ano maly exi sts
.
, ,
h ere for the rate of solub ility of th ese sul phi des is only very slow
,
o res ) is often very disturbing ; for exam ple pure platinum solu ,
tions are not precipitated by soda or barium carb onate but if iron ,
p l at i n um p r i
,
n ci p a ll y p a ll ad ium rhod ium and
,
i r i d ium wh il e,
the i r i dos ,
mine as i ts nam e indic ates c ons i sts m ai nly of i ri d ium and os mium
, , .
p ounds w i th a mm on ium c h l or i de wh ic h i n t u rn
,
are red uc ed to the
m eta l for m by i gn i t i on Howe ver i f the so lu t i on of the c ru de pl at in um
.
,
p l at i n um and ,
i n order
,
to wor k i t u p a fu r t h e r c o m pl icat e d p rocedure
, .
i s ne c essary .
R u t h en i u m .
a ci d.
I t s c ond uc t re mi nds one of potass ium m anganate for u nder the i nflu en c e ,
R uO 4,
wh ic h v o l at iliz es when c hl or i ne i s passed i nto the c on c entrated
s o lu t i on of potass ium r u thenate I t ca n b e so li d ifi ed by c oo li ng when
.
,
rutheni um .
t h e h i ghes t o xi des Thu s fus i on wi th c a ust ic potash and salt petre pro
.
R h o diu m .
The m etal i n the fu sed state has the a ppearan c e of al um inium and
is j u st as e x tens i b l e ( m a ll eab l e and d uc t il e ) as s ilver I t i s pre pared .
R h ( N H3 ) 5 C l 3 ( cf
. N e i ther ac i ds nor a qu a regi a affe c t i t When .
therm o c o upl e for m eas u ring h igh te mperat ures is m ade of pure plat inum
a n d an a ll oy of pl at i num a n d rho dium .
4 84 I N O R G A N I C C H E M I S TR Y .
l§ § 3 14
This very refractory m eta l i s obta ine d fro m iridosmine by heat ing i n a ”
c urrent of o xygen when the os mium v o lat iliz es as tetroxi de I n the form
,
“
c ru cibl es d i shes di st illing vesse ls for the c oncentrat i on of s ul phu ri c a ci d
, ,
Ir C l4 2K C l
~
Th e for m er d i sso lves in water readil y the l atter wi th
.
,
Pall adi u m .
m etalli c lustre reappears The m ost pec uliar chara c ter isti c of the
.
m etal i s i ts ab ili ty to abs orb hydr ogen in l arge qu ant it ies (occlu sion )
. .
heat i ng in a va c uum .
Pall ad ium form s two ser i es of c o m po unds the O u s PdX and the ,
-
z,
-
ic PdX
,
A c haracter i st ic c o mp o und of the fi rst seri es is p a ll ad i o u s
4.
u sed to separate i od ine fro m t h e other hal ogens s in c e thei r pall ad ium ,
the s odium platinic chl oride being very soluble even in alcohol , .
sodium hydroxide and then with acetic acid pl ati n u m h ydr oxi de , ,
Pt ( O H) 4 is precip itated ,
I t is soluble in strong acids and also in .
t o it (pla tin ic a cid) Salts of this acid are m oreover formed when
.
3 H2 O Ba Pt (C N ) 4 4 H2 O etc
,
The latter has come int o prominence
-
,
.
d ouble salts are noted for their beautiful col ors and strong dichroism .
METAL AMMO N IA -
C O M PO UN DS S EXTEN SI O N S . WER N ER ’
OF
THE N O TI O N O F VA L EN C E .
3 7 1 . Se ve ral
m e t al n o t a b l y t h o e o f t h
s, e e igh th g ro u p o f t h e pe ri o di c s
s y t e m a e c ap b l e
s ,
r f f rm in g c mpl e x c o mpound w i th ammon i a an d a ci d
a o o o s
p a re d b y t h e l d m a t e r oB ER ZE LI U Ss Th e t u dy o f t h e se
, u b t c e o ccu i
p ed . s s s an s
I n re c e nt y e ars h ow e ve r t h i fie l d h as b e n e xpl o e d
, , d g e atly e xte de d
s e r an r n
b y t h e i ve t ig t ions f W ERNER a d h i p u p il
n s a o o th t a t t h e p r e t t ime n s s, s a es n
o ve r 1 7 00 c o m po un ds f t h e g en r l t ype M Xp ( A m ) q a e al e dy k n ow n
o e a , r r a ,
ba e (s e v e n w t r)
or C h i f c re di t is al o d e WERNER f r h avi g t ake n u p
a e . e s u o n
t h e th e r t ic l tu dy o f t h e re l t i o n h ip b e t w ee n t h e e c omp ou ds a d as
o e a s a s s s n n ,
i rg ic c omp o u d
no an e p ci lly t h e m pl x l t h ave be en e st ab lish e d
n s, s e a co e sa s, .
v e ry li tt l e f a g e e ral n t ure c n ye t b e s t te d
o n It is re ad ily ap pre ci ated
a a a .
. 4 87
w e m ay fir s t e x ami n e t h e t in it it o t iam m in e c b al t r r r o ,
p o u n d i a no
s e l e ctro lyt e :
n -
fu rthermore fro m t h e fa c t th at t h e a c t i o n o f ,
a e n t h e l d b y t h e a ci d rad ic l
r o prese nt in t h e m o l e cul e fo b y ene rg et i c a s , r
r e a c t i o s i t is po
n ib le to s ub t itute oth er a ci d radic al for th ese w ith out
ss s s
li b erat in g t h e ammoni a mole cule s Th e s uppo it ion o f an act ive part icipa . s
s
s re a r .
exten si n o f t h e
o p en t n t i n f v
r es l en c C o b alt fo e x mple is at mo st
o o o a e .
,
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a umpt ion that t h e adde d ammoni a mole cul e di pl ce
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ar e n o t j o i n e d t o a de fi n ite e l e m e n t al ato m .
e l e ment s b o ro n c ar bo n
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an d n itro g e n, it is 4 , .
4 90 I N O R GA N I C C HE M I S TR Y .
3 18 .
n o n c on duc tor
-
If t h e s u b st i t u ti on is c arri e d furt he r as in N o s 5 6 an d 7
. .
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FI G 7 7 . .
amm o n i d h yd t
as anI t i a ig ific t fac t th at f
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o f a lts f me t l w h ic h give h e x mm in e
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s
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p o u n d es d e r
ariv d f m t h e h e x mmi e
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tw oN H mol e cul e f
3
-
w te w h ich c omp u n d
s orcor po d in b h vi or
a r, o s re s n e a
HgO .
Aq uo p e n t am m in e
c h ro m ic c h l o ri de
Th e a dd it i o f
onter h as t h e o ppo s ite e ffe ct Th e trich l oro t r iam m in e
wa .
c ob alt for ,
e x amp l e
is kn ow n t o form h yd at e s w ith 1 2 an d 3 mo l s w ate r
,
r , , . .
o n e an d in t h e an h ydrou s c o m p o u n d n o n e w e ar e ju st ifie d in as cr i b in g t o
,
th em in t h e fo llow in g co n st ituti on
C o ( H2 0 ) 012, an d Co
( N H3 ) 3 ( N H3 ) 3
013 ,
Bl ue h e xahy d r at e
w at e r in th e s e c o mpo u n ds c o rre s po n ds p e r fe c tl y t o th at o f t h e w at e r in t h e
a qu o s alt s o f t h e c o b al t ammo n i as i e
-
w i th t h e re l e as e o f e ac h w at er mol e
,
. .
,
~
o n t w o m o l e cul e s o f t h e w at e r a n d g o e s o ve r i n to t h e gr ee n h y drate ,
w h ic h is th u s i s o me r ic w i th t h e b lu e h ydrate Th e .
g r ee ri h y d r at e m o re,
o ve r c o n t ai n s o n l,y o n e c h l or i n e a t o m t h at c a n b e p re
h as c ll e d it h ydrat e
a is o m erism .
V i u c
ar o a es s f i ms e r i om t h t
so a m e ts w i th in t
a h e mre t l mm o a e a -
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l at in d i amm ine c o m p o u n d s a n d h a v e b e e n k n o w n s in c e 1 87 0 L ate r in .
I
I
f
I
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FI G 7 8 . . FI G 7 9 . .
v e st igat io n s ha ve sh o w n th at th i s kina
isomeri m o ccurs o ly w ith c o m of s n
u e type M
g um t i t r or m t at t h e
z
p o n ds f t h o T h e a p o n c an h.e e f e b e a de ssh
4
b ee n ab le t pre p ar s uc h i me r
o e so s .
tric h lori de 23 3 , B as e s, 3 9 , 1 02
tri oxi de 23 4 ,
BA S ILI
US VA ENT NU S, 23 1 L I
tri sulp hi de 23 6 ,
B AU M E de rees , 1 42 g
An tim on y l 2 3 5 ,
Ba uxi
te, 43 6 , 43 8
A nti se p tic 4 1 6 ,
BE CK
ER, 1 2 9
An gle s i te 286 ,
C
B E Q UERE , 3 9 7 L
A n g strom 3 9 2
Be ll m
e ta , 2 7 6 l
B ER M ANN , 9 9
G
,
A p atite 1 99 3 7 6
, ,
B E R NT H SE N , 1 3 3
A qu a re gi a 1 98 ,
Ar agon i te 3 7 6 3 82
Ar genti te 3 59
, ,
L
B ERT H E O T s pr n p e , 1 57
’
i ci l
B ER T H E O T— L
M A H ER a or etrL c l im ic
,
Argon 1 7 0 3 00 3 09
,
Ar gyr odi te 2 86
, ,
m
b o b , 1 53
A R I STO T L E 3 7 1
,
l
Bery , 3 7 2
A RR HEN I U S 95 1 01
,
B ery i ll um
,
3 03 , 3 7 2
Ars en ic 22 1 ,
, ,
LI
B ER ZE U S , 2 3 , 2 9 , 3 0, 1 4 8, 280, 2 9 3 ,
ac d,i 22 9
BE SS E M ER pro e ss , 4 6 9 c
m l e a , 22 6
B im l cul
o e ar rea t on s , ci
2 06 , 2 55
oxi de , 228
s ulphi des 2 2 9 2 68
I K L
B R E AND , 1 9 1
s ulp h o alts 2 3 0 s
, ,
B s i muth , 2 3 6
c l i
-
h or de , 2 3 7
,
Arse n i —
,
tun gstat s 4 57
,
e
xi
h y dr o des , 23 8
Ar se n i u s a ci d 22 8
o
,
xi
o des , 23 8
oxi d 226 e,
,
x c l i
o y h or de , 2 3 7
Ar seno li te 221
u i
s b n tr ate , 2 3 9
A rsen op yri te 2 2 1
,
s ul
ph ate , 2 3 9
Ars ine 22 3
,
s ul i
ph de s , 2 3 9
,
A sb e sto s , 3 7 4
B a l ck as h , 3 1 9
ci i
A sso at on, 82 , 1 85
l c
B an fixe , 3 88
m
A t o sp h ere , 1 65
"
,
l c
B ast furna e , 4 6 3
eac h in g , 3 6 ,” 6 1 2 6
A tomic h eat, 2 89
theory, 27 gl e ac h in g p o w e r , 85 3 8Q/
-
3
v lum
o e , 29 7
l
B ende, 407 z /
ig
w e h ts, 2 9
l m
B oo s , 4 7 1
D etermin at i on of 44 , 4 7 , 4 9 , 2 88, B O DEN ST E N , 1 5 I
3 05 il g i
B o in p o nt , e e at on o f, 6 1 , 2 7 2
-
lv i
B O L TW O O D , 404
l
T ab e , o f, I n s ide back cover
B O NE , 2 49
m
A to s , 28 , 4 9
l ck
B oneb a , 2 44
A ugi te, 3 7 4
ci
Bora te , 4 3 2
u ic c m u
A r o po nds, 3 7 0
x
Bora , 4 3 2 , 43 5
u u c m
A ro s o pou n ds , 3 6 9
ic ci
Bor a d, 4 3 3
u um
A r m u siv u m , 2 8 1
Boron, 4 3 2
A v o G A D R o s hyp oth e s s, 44, 60, 2 9 3
’
i I G L
B O U SS N AU T , 1 6 6
zi
A des , 1 7 9
BO EYL
zu i
A r te, 3 53
BO YL
E S l aw , 4 7 , 58, 1 60, 2 95
B RAND , 1 9 9
c
Ba ter a, 1 9 4i Brass , 3 5 5
Y
BAE ER , 1 44 Br ick
s , 440
K
BA ER , 1 85, 3 3 3 , 4 1 4 Br im
sto n e , 1 03
BA L A R D , 6 5 , 84 Bro ne, 6 5mi
B A M ER , 3 9 2 , 3 93
L x g
o y en o po n ds of, 9 0 c m u
i
B ar te , 3 87 z
Br on e , p h osp h or,
Bar ium , 3 87 s ilic
on, 2 7 6
IN D E X .
Bron es , 2 7 6z C ations , 96
Brook t e , 44 6 i C at s e y e , 4 55
-
C ae s ium , 3
29 i
C er te, 44 3
I
C A N , 24 9 iu
C er m , 44 5
l mi
C a a ne , 407 u i
C er ss te, 2 8 1
lci i g
C a n n , 3 53 , 46 3 lc ci
C h a o te, 3 53
lci
C a te, 3 7 6 , 3 82 C h a op yrite,
lc
Ca lcium , 3 7
6 C ha , 3 7 6 lk
c i
ar b de , 1 7 1 , 2 4 9 C h a ae eon m l mi nera e , 46 1 l
c ar b onate , 3 82 m
C h a b er a d, ci 3 19
c l i
h or de , 3 2 1 , 3 4 0, 3 79 c l
rysta s , 1 9 5
c imi
yan de, 1 7 5 c l
C har o a , 24 5
flu i or de , 3 80 C H A R PY , 4 66
xi
hydro de, 3 7 8 mc l fi
C h e i a af nity,
c l i
h yp o h or te , 3 80 operations 5 ,
m g i
an an te , 4 60 C hem i stry fi eld o f 3 , ,
i
n trate, 3 82 C h ili saltpetre 6 9 1 89 ,
xi
o de, 3 7 7 ,
i
p erox de, 3 7 9 C hl oramine 1 7 7 ,
il c
s i ate, 3 84 C hl oric acid 88 ,
l ic c
C a or e ffe t , 1 52 , 3 3 6 , 3 57 , 43 7 hydrate 3 7 ,
l im
C a or et er, 1 53 oxygen comp oun ds of 83 ,
lx
C a , 1 65 C h lorous aci d 88 ,
l
C ana r ays , 4 00 C h lorosulphon ic a cid 1 42 ,
C ar at , 3 68 C h l orpl at in ic a d, 4 85 ci
i
C arb des , 24 7 , 24 9 , 4 57 m
C hr o ates , 4 52
C arb on, 2 4 1 m
C hr o e a m , 4 52 lu
m u
a orph o s , 2 44 g
reen, 4 50
i xi
d o de , 2 52 llow 454
ye ,
x ul i
o ys ph de , 2 5 1 C h om ic anh ydri de 4 52
r ,
t e t r afl u o r id e , 24 7 chl oride 4 5 1 ,
C arb or nd u , 24 7 u m C hr om ite 44 9 4 50 , ,
ll
C arna ite , 3 2 2 , 3 2 9 , 3 7 4 , 4 4 1
‘
in stee l 4 7 1 ,
’
C A R o s a d, 1 44 ci oxy chl o i de 455 r ,
i
C ass ope m , 446 iu C hromous c omp oun ds 450 ,
i
C ass terite, 2 7 4 C h romyl ch lori de 4 55 ,
i
C as t ron, 4 66 C h y sob ery l 3 7 2
r .
C A s rN E R , pro ess , 3 1 4
'
c C i n b ar 1 03 4 1 0
na , ,
l i
C ata ys s , 3 4, 55, 7 3 , 1 29 , 1 3 4 , 1 3 7 , C L AR K E 3 8 6 ,
C l ay 4 3 6 440
, ,
4 96 I N DE X .
C o lc oth ar , 4 7 4 C URT I U S , 1 7 8
C o ld h o t tub e o f D E VILL E , 1 2 8
-
C y an i de pro c e ss , 3 60,
C o le m ani te 4 3 2 , 43 5 ,
C y a n ogen, 2 55
C o ll argo l , 2 69
o ll o ids , 2 6 6 , 268 , 3 6 5 , 4 3 8, 4 7 4 AL TO N27 , 43 , 293 , 3 97
,
C olumb ium , 44 9 A N IE LL e , 42 0 c ll
C omb u sti on, 1 1 , 1 6 5 VY
D A , 2 4 1 , 2 58, 3 1 1 , 3 22 , 4 1 8
C omp o n ents , 1 1 0 C
D EA O N pro e s s ( h or ne ) , 3 4 c c l i
C o mp o u n d , 2 5 D E B I E R N E , 3 98
C o n denser , 6 c
D e a n t at o n , 5 i
C onduc t ivity, mol e cul ar, 9 7 c
D e ay o f e e ent s , 4 02 , 4 04 lm
C onservati o n o f m atter, 1 6 e fi n it e p ro p ort ons , l aw o f, 2 7 i
en e rgy 1 5 3 ,
e gr e e o f fre e do ,
111 m
C on s tancy o f n atur al p h e n om ena ,
e liq u e s c e n c e , 3 1 8
C on t ac t a c t i o n Se e C atalysi s “
. . DE M O C R I T E s , 2 8
p ro c e ss ( s ul p hur ic a ci d ) 1 37 ,
l gi ic
D e p h o s t ate d air, 1 6 6
C onv erter 4 6 9 ,
De s icc
ators , 1 42
C oord inati on numb er 488 , e t o n at in g g as , 1 5 , 22 -
C o p p e r 3 53
,
E VILL
E , STE C A RE , 7 3 , 1 27 . L I
ammon i a c o mp ounds 3 5 9 D E WAR , 1 4 , 1 7 2
“
,
c om p o u n ds 3 5 5 ,
i l i
D a ys s , 2 66 , 2 6 9
(Se e C upric an d C uprous . i mi
D a de , 1 7 7
C opp eras 47 3 ,
i m
D a on d, 24 1
C orros ive s ub lim ate 41 4 4 1 5 , ,
D dy i mium ,
445
C orundum 4 3 6 , il m
D ato e ter, 1 08
C oun ter current pri ncip le 1 9
-
, ii ci
D s nfe t on, 3 6 ,
C O URT O I S 6 9 ,
isp e r s e , p h ase , e t c , 2 7 2 .
C ov e r i n g p o w e r 2 8 7 , 121,
C R E D N E R , 1 68
c i
C ro o te , 2 8 1 , 449 2 59 , 2 7 7 , 2 86 1 3 3 3 , 3 55, 3 7 0, 3 83 ,
C R O O K E s , 44 2
Cr uci l c
b e p r o ess ( stee ) , 4 7 0 l e lectrolytic ,
9 4, 1 3 1 ,
ic
C ryohydr p o nt , 3 3 9 , 3 41 , 3 7 9 i 2 68,
C ryohydrate, 3 3 9 , 3 43 4 09 , 4 1 5, 4 1 7 , 4 7 2 , 4 7 5, 4 7 8,
l
C ryo ite, 3 1 1 , 4 3 6 4 89 .
C ry os o p c ic m e th o d, 6 5 h d y ro lytic,
1 00 , 207 , 2 6 9 , 2 7 7 , 2 7 9
r y s t al liz at io n , 6
l i
C rystal o ds , 2 68 4 42 , 4 4 7 , 4 7 4
mix
r y s t al s , ed , 468 i
tens on, 4 3 0
u p an d c one ap parat s , 4 63 u is t ill at io n , 6 , 1 9
u ll i
C pe at on , 3 6 0, 3 6 8, 3 69 ci l
fra t on a , 6
u ic
C pr arsenite, 3 59 i i ui
D str b t on l aw o f BER TH E LO T , 3 25,
b ro mi de, 3 58
carb onate , 3 59 it hio n ic 1 45 a cid ,
c l i
h or de , 3 58 iv i
D ar ant syste , 1 1 4 m
xi
h ydro de , 3 58 I
D X O N , 2 55
i i
od de , 3 58 DO E B E R E I N E R , 2 1 2
i
n trate , 3 59 l mi
D o o te , 3 7 4
o xi de , 3 58 D oub l e de c omp os i ti on ,
41
4 98 IN DE X .
G o ld p lating 3 68
-
,
Hydr o c arb ons, 2 4 8
G O L D S C HM I D T reducti on m eth o d 4 3 7 , ,
Hydro ch loric a ci d, 3 7
compos ition o f
41 ,
L
G O D STE N , 4 00 I Hy dro fl u ob o ric a d, 4 3 3 ci
u i
G rad at on s a t pro es s, 3 1 5 l c Hy dro fl u o ric a d, 8 1 ci
G RA HAM , 2 6 6 , 2 68 Hy dr ofl u osil ic ic a d, 2 64 ci
G ra m quiv l
e a ent, 1 4 6 gl
Hydro e , 9 7 0, 3 58, 43 8, 4 50, 4 7 4
mole cule 3 2 ,
Hydro en, 1 3 g
G r p h ite 2 44
a ,
i
ant m on ide , 2 3 2
G raph itic a ci d 244 ,
i
arsen de , 22 3
G R I E SH E I M pro c e s 3 1 3 3 2 5 s , ,
mi
b ro de, 67
G RO VE s g b ttery 4 2 5
’
as a ,
c l i
h or de , 3 7
G U I G N E T S gr n 4 50
’
ee ,
. c i
yan de, 256
G u n m etal 2 7 6
-
,
i ul i
d s p h de , 1 2 0
G u n p ow d e r 2 6 3 2 7 , ,
lu i
f or de , 8 1
G U T E I T S t es t ( ar e ni c ) 222 i i
od de, 7 1
’
Z s , ,
2 24
G U YE 29 4 ,
xi
p ero de , 5 3 , 64 , 3 67 , 4 55
G Y P SUM 1 03 3 7 6 3 81, , ,
ul
p ers p hide , 1 2 0
i
p h o sph de , 2 04
Hali te, 3 1 1 l i
se en de , 1 4 9
HALL pro c e s s ( aluminium ) , 43 6 s ilicide , 2 62
H amm er s c al e 1 2 ,
s ul i
ph de, 1 1 5
HA M P S O N , 1 0, 1 7 0 llu i
te r de, 1 50
Har dn ess o f w ater, 3 83 i ul i
tr s p h de , 1 2
HAR G REAVE S m eth o d, 3 1 7
’
Hydro lys i s Se e D i sso ci ati on hydro
.
,
Hartsh orn, salt o f, 3 3 4 lyti c ;
Hausm anni te , 4 58 Hydroso l 2 7 0 ,
He at ato mic , 29 0
,
Hyd oxy l 1 4 3
r ,
mole cul ar 1 7 3 2 91 , ,
Hydroxyl mi n e 1 80 a ,
o f d iluti on 1 53 ,
di sulp h onic a ci d 1 98
-
formati on 1 52 1 55 , ,
Hypo , 1 3 2 , 3 1 7
n eutraliz at i on 1 5 3 3 50 , ,
Hyp o c h loro us a ci d, 84
s o lu ti on 1 53 1 61 3 3 6 , , ,
oxi de 84 ,
Sp e cific 2 90 ,
Hypon itrou s a ci d 1 87 ,
He vy sp
a 3 87 ar , Hypoph os p h oric a ci d 2 1 8 ,
He lium 1 7 9 3 00 3 9 4 4 00 4 02
, , , , ,
Hypop h osphorou s a ci d 220 ,
HE LM H O LT Z 1 58 ,
Hypo sulp h ur o us aci d 1 3 3 ,
Hem t ite 4 63
a ,
Hyp oth es i s 2 ,
HENR Y S l aw 1 1 3 9 9 5 1 3 3 3 3 2
’
, , , , , ,
43 4
Hep ar su lp h ur is , 3 2 8 I ce m c
a hine , 1 7 5
-
HER O U LT , 4 3 6 I c e ston e , 3 1 1 , 4 3 6
furn ace 470 ,
Il lumi i g
nat n g as , 4 7 6
HE SS ,
l aw o f, 1 53 c
I n andes ent e e tr c l c ic lig
h t , 4 56
Hexammine c ob alt s alts, 489 ig LB C
g as l h t ( W E S A H ) , 44 3
Hi ttorf 202 ,
i l
Inde l b e in k , 3 6 6
HO FM ANN , 2 4 ic
Ind ators , 3 50, 3 5 9
Holmium , 44 3 Ind ium , 3 05 ,
44 1
Hop p er c r y stal of s al t 3 1 7 ,
uc c ivi
I nd e d r adi o a t t y , 4 01
-
Hor n b l ende 3 7 4 ,
v i i
I n ers on , p o nt , o f, 1 06
Horn Silv er 3 59 3 6 3 , ,
i
I o d ne, 6 9
H ub n erite 4 56 ,
c l i
h or des , 83
Hydra te i so meri sm , 19 2 x g c m u
o y en o p o n ds o f, 9 1
Hydrate s 4 90 ,
m
I o do e try, 226 , 2 28
Hydraulic mi n ing , 3 68 I on ic quili ium
e br , 98
Hydrazin e 1 7 7 ,
qu i
e at on , 1 1 8 , 1 3 2 , 2 7 7 , 282 ,
Hy draz oic aci d, 1 7 8
I N D EX
i
’ 3 56 , ch lori de 285
1
,
4 5 1 453 , 4 5 9 , chromat e 4 54 ,
v l c
a en e o f, 1 2 3 glas 3 84 s,
i ium
Ir d ,
4 84 ni trate 2 86 ,
i i
Ir do s m n e, 4 82 , 484 oxi de s 2 83 ,
Ir on, 4 6 3 p eroxi de 9 9 4 4 22 , ,
an d carb on m xide
ono ,
47 7 p ersul p h at e 2 86 ,
w h ite 2 86
,
Kain i te 3 22 3 7 4 L E C L A N C H E e l , 4 23 cl
, ,
L E C O Q DE B O I SB A U D R A N , 44 1
Kaolin 4 3 6 440, ,
i l
L ep do ite , 3 1 0, 3 2 9
KA SS NER pro cess 285 , ,
L EU PPU S , 2 8 CI
KA Y SER 3 92 3 9 3 , ,
L E Y D E N FR O ST , pheno en on, 1 7 0 m
K e lp 6 9
,
im
L e, 3 7 7
Ki e serite 3 7 4 ul u lu i
ph r s o t on , 3 8 1
,
KI PP generator 1 1 5
,
im
L e stone , 24 1 , 3 7 6
K I R CH O FF 3 2 9 3 89 3 9 1
,
3 98
I
L ND E, 1 0, 1 7 0
K N I ET S C H , 1 3 7
, , , ,
L iqu i
at on , 2 7 4
K O HL RAU S C H 19
L iqu c i x g
efa t on of o y en, 1 0
KO PP 2 9 1
,
i g
L thar e , 2 83
K RY PT O N
,
L th a i i mic a , 3 1 0, 3 2 9
K DH N E method
,
26 1
L thi i um ,
3 10
,
Y Y
L O R R DE B RU N , 1 7 8, 2 7 2
LO CKY
ER , 1 7 2
L ab il e, 1 08 u c u ic
L nar a st , 3 66
B G
L AD EN UR , 5 3 ~
L 11 p c ll
e , 42 3
m l ck
L a pb a , 2 4 5 L te u cium ,
4 43
L anthan um ,
44 5
i l zuli
L ap s a ,
4 40
V II
L A O S ER , 1 0, 1 3 , 1 8, 1 6 5, 2 4 1 M agn alium , 4 3 7
V G
L aw o f A O ADR O , 44, 4 7 , 60, 2 93 M agnesi a , 3 7 4
BO YL E See BO E S l aw ’
. YL . lb 3 7 6
a a,
n o m en a , 3 u sta 3 7 4 ,
i i ui
d str b t on ( B ER T H E O T ) , 3 25 L mmonium ph osphate
a , 3 76
339 b ori de 43 2 ,
L G
D U O N an d PE T T , 2 90, 4 07 I c rb on ate 3 7 6
a ,
G A Y L U SSA , 4 3 , 4 7 58
-
C chloride 3 7 5 ,
HENR Y
Se e H ENR S l aw
’
. Y . hydroxi de 3 7 4 ,
HE S S , 1 53 ni tri de 1 7 4 3 7 4 , ,
M IT SC H E R L I C H , 2 9 2 oxi de 3 7 4 ,
mul i l
t p e proport ons , 2 9 i sulph ate 3 7 6 ,
c mic l m
he a as s a t on , 7 5 ci M agn etite 4 6 3 4 7 4 , ,
N EU M ANN , 2 9 1 M l c h i te 3 5 3
a a ,
c v
o ta e s , 2 9 6 M ll ab le iron 4 66
a e ,
m
t her one tra ity, 3 50, 4 1 5 u l M AN C HO T 55 ,
00 I N D EX .
I TS C H E R L I C H s
in t l 47 1 s ee ,
te st 203 ,
M an g anic c ompoun ds ,
4 59 M i xtur e 1 69 ,
cid 46 0
a ,
M ob ile equilib rium V A N ,
’
T HO FF ’
S
M ang nou c omp ounds
a s ,
4 59 pr inci p le o f 1 6 0 3 3 6 , ,
M arb l e 3 7 6 O H R s s a lt 4 7 3
’
, ,
M A R C K W A L D , 3 99 M O I SSAN 1 6 3 8 6 7
2
, , , ,
M ar l , 3 7 6 24 4 , 2 4 7 , 4 4 6 44 9
M arsh g as , 2 4 8 ol e, 3 2
,
1 22 , 3 42 , 4 1 2 , i xi
tr o de, 455
4 67 o l y bdic a d , 4 56 ci
M E N D E L i E FF, 2 96 , 2 9 9 , 3 03 , 3 07 , 4 4 1 , o n a z it e sand, 4 4 3
44 5 M o n ob a s a d , 8 3 ic ci
M E N D E L EE FF S ’
tab le (peri odic sy s L Y
M O R E , 2 9 , 2 1 2 , 294
t e m ) , 3 01 M ortar , 3 7 8
M E N S C H I N G , 23 2 M os a ic g l
o d, 2 8 1
M ercur ic ammon ium chlori de ,
414 u i ic ci
M r at a d, 3 8
c h loride 4 1 4 ,
M UT HM A N N , 4 56
cy i de 2 6 8 4 1 4
an , ,
h ali de lk ali 4 1 5
s, a ,
c
N as en t state, 3 7 , 5 4
iodide 4 1 5 ,
u l
N at r a g as , 24 8
n i tr t e 4 1 6
a , g iv
N e at e ( photo raphy) , 3 65 g
oxid 9 408 e, ,
N eody mium ,
44 5
sul ph te 4 1 6 a ,
N eon
s ulp h i de 4 1 7 ,
N ERN S T , 1 04 , 1 84 ,
M rcurou s c omp ounds 4 1 3
e ,
gl ow er,’ 5 1 , 54
M rcur y 4 1 0
e , L
N E S S ER S s o t on, 4 1 5 lu i
M e oth orium 44 8
s ,
’
N E UM A N N S l aw , 2 9 1
M etal ammoni a c omp ounds
-
,
4 86 N E W AND S , 2 9 6
L
M e t l lo i ds 8
a ,
N E W TO N S
’
m
eta , 23 7 l
M e t llur gy o f iron 4 63
a ,
N ic c o lit e , 4 7 9
M t p h o sp h oric aci d 2 1 7
e a , N ick l e , 47 9
M tap h o p h orous aci d 2 1 9
e s , l
s te e , 4 7 1
M e tastab le ystem 1 08 3 4 6 s , , i ium
N ob ,
4 49
M e tastannic aci d 2 80 ,
i
N ton , 4 02
M eth ane, 24 8 N it r am ide , 1 99
M ethyl orange, 3 53 it ric a d , 1 89 ci
M E Y ER , L O T H AR , 4 1 , 2 96 , 3 00, 3 08 xi
o de , 1 83
M E Y ER , VIC T O R , 2 3 2 it r ides , 1 6 4
M ic a, 4 3 6 it r il o su l p h o n a t es, 1 9 8
M IC H E L SO N , 3 9 2 i t ro g e n , 1 6 2 1 7 0
,
M icro c o smi c s alt , 3 3 4 a d derci iv iv
at es of, 1 9 5
M i n er aliz ati on of org anic matter , 1 6 8 i xi
d o de , 1 85
M i n er s s afety l amp , 2 58
’
l g c m u
h a o en o po nds of, 1 7 9
M i n ium, 2 84 g m u
1: y o ro en c o p o nds o f, 1 7 4