Ele c trical Wor l d d

The Enginee ring an ing Journal

En i nee r i ng N ew
g s

R a ilway Age G a ze tte

S i gn a l E n
g i ne e r

Elec tr i c R a ilway Jo ur na l
 A y Li b ri Dell a
dd
T he ssa er . -Fr o m Pir otech nia . Li Di ece Pir o tec h nia , b y V a nnuccio
Bit ing occio. V enice. M D L VIII — ( 3r
. e ition) .
 A MA N UA L

FI R E A S S A Y I N G

CHA R LE S HER M A N FULT ON, E M , D S o . . . .

P ROFE S S O R Ol “T A LLU BG Y CA S E S CHOO L OI A PPLI E D S CI EN

'
.
'
CE .

S ECON D E DI TI ON

EN I RT E LY R E w m r rE N
' '
A ND EN LA R G E D
S EC ON D I u a ssx o n

M CG R A W —HILL BOOK COM PA N Y , IN C .

23 9 WE S T 3 9T H S T RE E T , N E W Y OR K
6 BOUV ERI E S T R EET LO N D O N , . E C
. .

191 1
 COPYR I G HT ,
1 90 7, BY TH E HI L L PU B LI S H IN G CO .

C Y
OP T,
R IG H 19 1 1, BY MOG HA w Hrm.
- B OOK COM PA N Y .

P r i nte dda n E l ec tr otype dby

7 71 6 A l a p l e P r ess
Yo r k . Pa .
 t o h is {b ot her
T HI S B OOK I S LO V IN G LY D E D C T E D
I A BY

T HE A U TH OR
 PR E FA CE T O T HE S E COND E D I T I ON

R ecent progress in A ss a ying h a s m a de it desir a ble to a d

d
d
to
the boo k a n revise it
d
.

The subj ects Of a ss a y furn a ces a ss a y flu x es cu p ell a tion a n

, ,

d
speci a l meth o ds Of a ss a y h a ve bee n a dded to .

The a uth o r d esires to e x press his th a nks to Mr W J S h a r w o o

d
. . .

f o r a ddition a l m a teri a l furni shed for the boo k a n for a se a rch

Of the first editi o n fo r errors .

d
H e a ls o a cknowledges the kindness Of Messrs J a y A Ca rp ent er
. .
,

E V a n L S mith 0 A A nderson a n others in furnishing new

. .
,
. .

m a te ri a l .

H e will a ppreci a t e gre a tly t he courtesy Of a ss a yers or met allu r

,

gists who will c a ll his a ttenti o n t o errors or p ertinent omissions

in this edition .

C HAR LES H FULTO N .

C LE V E LA N D OHI O
, ,

D ecember , 1 9 1 1 .
 PR E FA CE T O T HE FI R S T E D I T I ON

uthor h a s long recogni zed the need Of a work on fire

d
T he a

a ss a ying th a t tre a ts the subj ect from the scientific a n r a ti o n a l

p o int of view r a ther th a n fro m th a t Of the rul e Of thumb“ ”
.

S tr a ngely enough this l a st governs most modern works o n the

,

subj ect The book is closel y confined to the subj ect Of fire
.

d d
a s sa ying which it tre a ts in det a il
, The ch a p ters on R educti o n .

” “
Ox id a tion R e a ctions ”

d
an Crucible A ss a y a n A ss a y S l a gs, ,
“ ”
Cupell a tion outline s cientific a lly the princi p l es Of a ssa ying
d
an ,
.

A l a rge p a rt Of th ese ch a pters is new a n some Of the m a teri a l is

d
p resented for the first time The ch a pt er o n the E rrors in the .

”
A ss a y fo r G old a n S ilv er discusses the a ccur a cy Of the a ss a y,

in gre a t er d et a il th a n h a s b een a tt empted h eret ofo r e

d
.

T h e a uth o r h as h a e x pe r i en ce wi t h pr a ctic a lly all o f the

m ethods Of a ss a y described i n t h e b o o k ; first a s a m a nipul a tor
d
,

then a s a t ea cher a n fin a lly in ch a rge Of w o r ks The b oo k is

d
,
.

intended fo r the use Of stud ents in t echnic a l sch o o ls a n f o r the '

a ss a yer in a ctu a l d a ily p r a ctice w h o m a y feel the n eed o f a

r ef er ence b o ok .

The a utho r wishes to a cknowledge his ind ebt edness t o t h e

wr it ers cit ed in the t ex t especi al ly t o t h e l a t e Prof ess o r E H
d
. .
,

Miller Of Columbi a U niv er sity wh o s e work a n pe r s o n a l ity h a s

, ,

He a ls o ex presses his
d
ev er be en a n inspir a ti o n t o the a uth o r

d
.

th a nks t o Mr J B R ea d a n Mr Iv a n E G o odner c h emist a n

. . . . .
,

a ss a y er r esp ectiv ely fo r the S t a nd a rd S m elting Comp a ny R a pid

d
, ,

City a n t o Mr F r a nk Br y a nt his a ssist a nt a t the S cho ol Of

d
,
.
,

Mines fo r v al u a ble a i in the t esting Of methods ; to Professor

,

M F Co o lb a ugh fo r the inspecti o n Of those ch a pters c o nt a ining

d dd
. .

chemic al equ a ti o ns etc a n to Miss E thel S p a y e a n Miss

d
.
, ,

D ell a M H a ft for v a lu a bl e a i received in the p r ep a r a ti o n Of

.

the m a nuscript fo r public a tion The a uth o r a lso desires to ex .

press his a pprecia ti o n Of t h e c o urtesy Of t h e D env er Fire Cl a y

Co mp a ny a n o f A insw o rth d S o n D enver Color a d o Of F W
d d
. .
, , ,

B r a un a n Comp a ny Lo s A ngel es Ca lif o rni a a n Of o th ers

d
, , , ,

in furnishing ph o togr a phs a n el ectro typ es Of a pp a r a tus used in

the bo o k .

C HARLES H ER M A N FUL TO N .

R A PI D CI TY S D , . .
,

A pr il , 1 907 .
 CONT E NT S

PR E FA CE

C HAPTE R I
A SSA Y FU R N A CE S A ND TOOLS
Assa y F ur na ces . F u els . C l b ur ni ng M ums-F ur na ces
oa - .

Co nst r u ct i o n . Dimensio ns . Woo d-b ur ni ng F urna ce Co ke .

Fu rna ce Ga solene F urnace G a s F ur na ce Ca pa cit ies Of

d
. . .

Fur na ces a n Cost per Assa y fo r F uel w it h Diflerent F urna ces .

M u fies Fur na ce Tools To ngs et c M u lti ple S corifier To ngs

.
, , . .

pel Ch a r g i ng D evi ce Molds Cru cibles S corifiers

d
Cu . . .
,

R oa st i ng Dishes , et c . Cr ushi ng a n Pul veri zi ng Appa r a t us .

C HAPTE R II
D EFI N IT ON S ;
I R E A G E NT s ; .
E ASS Y
TH A or R E A G E N TS —
27 3 5
D efi nitions of Assa y g Gn Meth o d fo r t h e Determi
di
i n . e er a l

na t io n Of G old a n S l ver . R e a gents U d se in A s sa ying .

Assa y of R ea gents .

C HAPTE R III
S A M P LI N G 3 6—4 1
Meth o ds Of S a mpli ng Cla ssifi ca tion Of S a m pling Meth ods
d
. .

Princi ples Of S a m pli ng S a m pling in Mills a n S melters

d
. .

Co ni ng a n Q ua r teri ng S a mpli ng by A l ter na te S h o vel . .

S a mpli ng A ppa r a t us in t h e Assa y L a b o r a to r y Pr epa r a tio n .

Of th e Assa y S a m ple Co nt r ol Assa ys Um pire Assa ys

d
. . .

Mode Of S ettlement S a m pling Lea d a n Co pper B ullion

. .

C HAPTE R I V
WEI G HI N G ; BA LA N CE S
WE I G HTS A ND 4 2 52
-

T h e Assa y B a la nce Meth od Of Setti ng Up Co nstr uctio n

. . .

D iscussion of th e Princi ples Of th e B a la nce Sensibili t y . .

Weig g D etermina ti o n Of Lengt h

hi n . O f B a la nce a rm s
- P u lp .

B a la nce Pra cti ca l No tes o n th e A ssa y B a la nce Weights

. . .

T h e Assa y-t o n S ystem .

C HAPTE R V
R E D U CTI ON A ND OXI DA TI ON R E A CTI ON S —
53 6 3
R ed u c t i o n . Ox ida ti o n . R e d u cti o n Of Lea d fr om Lith a r ge
by Ar gol by Ca r bo n by Flo ur
, , , by S ul phides I nfl uence Of
.

X1
x ii C O N T E NTS
PA GES
S od a R ed ucti o n Of
. Lea d from Lea d S ili ca tes Ox ida ti on of .

I m p uri ties b y Niter Niter R ea ctions with R e d ucing Agents

d d
. .

R ea ct ion betw een Meta lli c Lea d a n Niter Niter a n

d
.

Ca r bon Niter a n P yri te I nfl uence of S ili ca o n th e

d
. .

R ea ct i ons Ch a r ges to D eter mi ne R e d ucing a n Ox idizi ng

d
.

Powers Ox i ing Pow er in Ores

. .

CHAPTE R VI
T HE CR U CI B LE ASSA Y ; ASSA Y S LA G S —
64 75
Na t ure of th e Cr uci ble Assa y I nfluence of Fineness of
d
.

Cr ush ing Mode of Occurrence of Gold a n S il ver Ph ysi ca l

.
,

Proper ties of t h e S la g Chemi ca l Pro per ties of th e S la g , .

Fo rma tion Temper a t ures of Assa y S la gs N a t ure of Assa y

d
.

S la gs a n th eir M o de Of F orma ti on I nfl uence o n t h e .

Assa y of th e Forma t ion Tem pera t ur e Co nstit uents of .

Assa y S la g s Cla ssifi ca tion b y S ili ca te Deg ree Influence of

d
. .

S i li ca te Degree a n Difierent B a ses o n Fo rma t i o n Tem pera

'

t u re . E utect i c Co m p osit io ns of S la gs Ta ble Of Assa y S la gs . .

Ta ble for th e Ca lcula tio n Of S la gs E x a m ple Of th e Ca lcula .

t i on of a n Assa y S la g Co m po si tio n of O res Assa y S la gs . .

Com mo nly Ma de Color of S la gs . .

C HAPTE R VII

C U P E LLA TI ON 76 1 06
-

O bject of Cupella ti on B o ne A sh C u pels Ma king Cupels . . .

Ma gnesia Cu pels Cement Cu pels Pro cess of Cu pella tio n

. . .

S pro uti ng o f B ea d s Freezi ng point Cur ves of Lea d S i l ver

d
.
- -

Lea d-Co pper Temper a t u re Of Cu pella ti on T h e Un

d
an . .

c o veri ng Freezi ng o f Lea d B ut t o ns Fea t h ers ”

an .

in Cu pella ti o n I nfl uence of I m puri ties o n t he Pr ocess of

.

Cu pella ti o n I nfl uence of Co pper I nfluence of Telluri um

. . .

Cu pella t ion wi t h C upels of Diflerent Ma te r ia .

C HAPTE R V III

PA R TI N G —

d
1 07 1 1 0
R a ti o of G ld t
S il ver ecessa r y to Pa r t w i th
o
'

o i t ri c N N Aci .

I nqua r ta ti on S t rength Of Acid Tem pera t ure of

. . Acid .

Pa r ting Devi ces A nnea ling . .

C HAPTE R I X
T HE ASSA Y OF OR E S CON TA IN IN G I MPUR I TI E S 1 1 1 13 0
-

Defi ni ti on of I m puri ties Com mon Im pu rit ies E fiect of . .

I m p uri ties on Assa y P ro d u ctio n Of a Ma tte E fiect of S i li ca

. . .

E ff ect of S o d a Ki nd Of I m p u rities S ta nda r d Met h o ds Of

. .

Assa y R o a sting
. N ite r Met h od Miller s O x ide S la g
. .
’
-

Meth od Per kins E x cess-li th a rge Meth od

. Ni ter-I ron
’
.
 C O N T E N TS xiii

d
P G A ES

Met ho N a t u re I r o n-
.Nai l Fusion T h e Cya nideof th e .

Met hod Com pa ri son of t h e Difierent Cr u cible Meth od s of

.

Assa y S corifica tio n S corifier s Am ount of Lea d used

. . . .

Amount of Ore Pr o cess Of S corifica tion Temper a t ure Of . .

S corifica tion R e scorifica tio n O r der of Ox ida t ion Of Meta ls

. . .

Appli ca bili ty of S corifica tion Co mbi na t i on Meth o d Fo r . .

B li ster Co pper For Ma t t es For Cya nide Preci pi ta tes . . .

Preca ut ions to be O bser ved in th e Meth od .

C HAPTE R X

S PE CI A L METH OD S OF ASSA Y —
1 3 1 1 59
Tell uride O res Assa y by Cri pple Creek Flux .By E x cess .

li t h a r ge Fl ux B eha vior Of Tell uri u m in th e F usion Amo unt

. .

of Tell u ri u m P resent in O res Losses Ca used by Tellu ri u m . .

Assa y of Co mplex Tellu rides w i th Difierent Flux es R e sults .

O bta i ned Assa y of COpper bea r ing Ma ter ia l By S corifica

- . .

t i on .R esult s O b ta i ned E ces li t h a r ge Meth o d for B li ster

x s- .

Copper By Cr u ci ble Assa y Assa y o f Ma teri a l Conta i ni ng

. .

Z inc E fiect of Z inc S corifica tion fo r Z i nc O res Cru cible

. . .

F usi on f or Z i nc O res Fo r Cy a ni de Preci pi ta tes Assa y of . .

Ma teri a l Co nta i ning G ra ph ite Assa y of Anti monia l G old-sil .

‘

ver O res Arseni ca l O r es Dimculties E x perienced wi th

. .

t hese O res Assa y of Hea vy S ulphides Assa y of Ma teri a l

. .

Conta i ni ng Meta c Assa y Of O res Co nt a ini ng Free

d
S ca les .

Gold T h e Assa y Of S la gs a n Cupels Ama lga ma tion Test

. .

to Det er m i ne F ree G old P resent Assa y Of Cya nide S olut io ns . .

Assa y of Ma teria l Co nta i ni ng Meta lli c I r on .

C HAPTE R XI
E R R OR S HE
ASSA Y F OR G OLD A N D SI LV E R
d
IN T 1 60 -1 73
Losses in t h e Cup ella t io n of Pu re S i lver Of P u re G el . .

How t h e Losses O ccur E ff ect o f Tem pera t u re I nfl uence of . .

Diff erent Types of Cu pels Cur ves S how i ng Cupella ti o n Loss .

Losses in th e Cupella ti on of G old S ilver Allo ys R e la ti ve

d
es.
- .

Amo unt Of Loss b y Abso r p ti on a n Vola tili za ti on S la g Loss

d
.

an C upel Absor p ti on in Tell u ride O res In Z i ncifer ous .

Ma teria l In Hi ghgr a de S il ver O res In Cu prifero us Ma te

. .

ri a l. Gener a l Discussion of Losses Other E rrors R e ten . .

tio n of Lea d o r Co pper in B ea ds R e t enti on of S il ver by Go ld

d
d
.

a f ter Pa rt i ng Loss of Gold by S olu tion in Acid O cclu e

. .

Ga ses E rror in Weig hi ng R e sum!

. . .

C HA PTE R XII
T HE ASSA Y or BU LI ONL -
1 7 1 85
4
Cla ssifi ca ti on of B ulli ons Assa y of Lea d B ulli o n T h e A s . .

sa y of S i l ver B ulli on Cu pella ti on Method Preli mi na ry Assa y

.
, ,
 C O NT E N T S
PA GE S
Ch eck Assa y R e gula r
G Assa y
-L ussa c M eth o d for S i l ver
y
d
, a .

B ullion S ta nda r diza tion of S olution, A a ra tus R e q uire ,

. pp
t h e A ssa y, Ca l cula t i ons T h e Assa y of ol d B ulli on fo r S il ver
. G
by a Wet Method T he Assa y of old B ullion Prelimina ry
. G .

Assa y, Ch eck Assa y, Proo f Alloys R e gula r Assa y Pre a ra p

d
. .

ti on Of Proo f old a n S il verG .

C HAP TE R XIII

T HE ASS A Y or OR E S A ND A LLOY S C ON TA IN I N G PLA TI N U M , ImDI U M .

G OLD, S I V E R , L ETC . 1 86 -1
92
Difi cul ty Assa y Co m positio n Of Pla tinum N u gg ets
of . .

Cu pella t i o n Of Lea d Co nta i ni ng Pla tinum etc Ap pea ra nce Of , .

Cu peled B ea d Action of Acids on Meta ls Conta i ned in t h e

.

Pla ti num-S il ver bea d Nitri c A ci d S ulph uri c Acid Nit ro

. .
,

h yd rochlo ri c A c d
‘ Meth o ds of Assa y to O bta in Lea d B utto n
. .

Fo r O res Co nt a i ni ng Met a lli c G ra i ns For A ll oys Met ho d Of . .

Assa y b y Pa r ti ng S il ver-Pla ti num Alloys in S ulph uri c Acid ,

et c. Meth o d of Assa y b y Di sso lvi ng Lea d B utton in Nitric

Acid R esults O bta i na ble
. .

C HAPTE R XI V

T HE AS SA Y or T I N , ME R C UR Y,
LE A D BI SMU TH A N D AN TIM ON Y , . 1 93—20 1
Gener a l R e ma r ks on th e Fire Assa y for B a se Meta ls T h e .

Assa y Of T i n O res Ca uses Of Loss in th e Assa y P repa ra

. .

t i o n Of t h e Or e for A s sa y T h e Cya nide M eth o d . T h e Ca r .

m a n Met h o d R esults O bta i na ble

. T h e Mer cur y Assa y A p . .

p a ra t us R e q uired T h e Cond u ct of th e A ssa y R esults

. .

O bta i na ble Assa y of Lea d O res I na c cu ra ci es o f it Lea d

. . .

Flux Meth od S od a -Ar go! Meth o d Cya nide Meth od R e a c

. . .

t i o ns in t h e Assa y R esu lt s O b ta i na ble T h e Assa y Of

d
. .

Anti mo ny a n Bi smuth Ores .

A p PE N DI x . 202-205
Co nversi o n Ta ble for Weights Ta ble of Assa y Va lua tio ns
d
. .

Ta ble o f Fi neness Of B ulli o n a n Alloy s of Precio us Meta l s

d di
.

Ta ble Of Vol ume a n Weight of Fi ne Gold a n S l ver .

I N DE x
 Q

H T w o-Mu ffle F u r na ce Perspec ti ve Vi ew

.

w T w o-Mu ffle Fur na ce Cro ss S ect i o n

.

w T w o Mu ffle F u rna ce
- Lo ng it u dina l S ect io n
.
-

e T h r ee M u m
— e F u r na ce C r o ss-S ecti o n
.

d
s T h r ee Mu ffle F u r na ce
- Lo ngi tu dina l S ecti o n
.

Oil b u rni ng F u r na ce
- Cross S ecti o n
.
-

fl Woo d -B u r ni ng M u ffle— F u r na ce Cr o ss-S ecti o n

.

m Woo d B ur ning Mu file—Furna ce Longit u di na l

- .

w Woo d B u r ni ng M u me—Fum a ce
-

M fi —
e F u r na c e f or B u r ni ng Co k e

d
1 0 u.

1 1 Co mbi na t io n M u fiie a n Po t F u r na c e
d
.

I2 Co m bi na t i o n M u ffle a n Po t F u r na c e
‘ ‘

1 3 G a so lene F u r na ce A pp a r a t u s
.

1 4 T h e Ca r y G a so lene B u r ner
d
.

1 5 G a so lene Ta nk a n Pu m p A ppa r a t u s
.

1 6 G a so lene-B u r ni ng Cr u cib le F u r na ce
.

1 7 G a so lene B u r ni ng M u tfie—
.
- F ur na ce .

1 8 Ca se-B u r ner
. .

19 Ca se G a s B u r ner
.
- .

2 0 M u ffle F u r na c e w i t h S p
. eci a l S u ppo r t s
2 1 G a s B u r ni ng Mu tfle F u r na ce
.
- -

2 2 Cr u cib le To ngs
. Undesir a ble Mo del
.

2 3 Cru cib le To ngs

.

24 Cupel T o ngs
.

2 5 S co ri fier To ngs
. .
o

2 6 S co rifier To ngs
.

2 7 M ul t i p le S co rifier To ngs ( Keller )

.

2 8 M u lti p le S c o rifier To ngs ( K eller )

.

2 9 Cupel Ch a r ging D e vi ce ( Keller )

.

3 0 C ru cib le P o u r i ng M ol ds
.

3 1 Cu pel T r a y
3 2 Fire-Cla y A nnea li n
.

. g Cup Tr a y - .

3 3 F i re-Cla y Cr u cib les

.

34 S co rifier s
d
.

35 . B u ck B oa r d a n M uller
36 . B uck B oa r d B r u sh es
37 . Jo nes Ri flie S a mp ler
38 . Umpire Ore Sa m pler
39 . D ia gra m Of Assa y B a la nce
40 . P ulp B a la nce
41 . Assa y B u t ton B a la nce
42 . N on Colum n Type Of Assa y B a la nce
-
x v i LI ST OF I LLUST RATI O N S
FI G .

43 . Pla tinum Assa y Weigh ts

44 . Assa y-T o n Weigh ts
45 . Gra m Weigh ts
46 . Freezi ng-Po i nt Cur ve R h o do ni te-Hyperst hene
.

C upel Ma chine
d
47
Freezi ng Po i nt Cur ve of L
.

48 .
- en S i l ver
-

Freezi ng P o i nt Cu r ve Of Lea d Co pper

d
49 .
- -

50 . Temper a t ure-Cu r ve Ai r in Muffle a n C upelling Lea d

,
-

51 . Tem per a t ure-Cur ve D u ri ng Cupella ti on S ho w i ng Unco veri ng

“F reezi ng Of B u tt o n
”

52 . T empera t u re Cu r ve Cupella t i o n Of Lea d S i l ver

,
-

53 . Tem per a t u re-Cu r ve Cu pella ti o n of Lea d S ilver

,
-

Tem pera t ure-Cur ve Cu pella tio n of Lea d S il ver

,
-

55 . Pa r t ing B a th
56 . Pa r ti ng Fla sk s
57 Ho mesta ke Agita tor
Cu r ve S h o w i ng S il ver-Losses In Cu pellati o n
.

58 .

59 . Je weller 8 R olls
’

60 . Appa ra t us R equir ed for Mercury Assa y

2 A M A N UAL OF FI RE ASSAYIN G

Coal , Coke dO Fur na ces —

d
il
d
an Fig 1 shows such a t w o . .

mu m e furn a ce in perspective a n F igs 2 a n 3 in cross-section

, .
, .

The essenti al p a rts o f the furna ce as the tiling A B L K etc , , , , , ,

.
,

ca n b e re a d ily purch a sed a lthough the interior o f the furn a c e

,

m a y a lso be built of fir e brick

d
- The tiling fu rn a ce h owever
.
, ,

i s mo re e a sily set up a n is more dur a ble In the design Of t h e .

soft co a l fu n ce the essenti a dimensio ns a e a re a of fir e gr a te ;

d
- r a ,
l r : -
.

ist a nce fro m the gra te t o the bottom of the lower mu m e ; t h e

”

d dd
fire sp a ce i a the dist a nce between ,
. .
,

mu mes an the side a n en w alls of

d
d
t h e furn a ce a n between the top Of th e ,

upper mu m e a n the roof Of the fu rn a ce ,

givi ng the proper sp a ce for combustion

of t h e g ases Th ese dimensions depend .

upon the n a ture Of the co al In Figs

d
. .

2 a n 3 the gra te dimensions a r e

x 2 1 0 in ; dist a nce from gr a te to lower
. .

muffle 18 in ; fire sp a ce in ; extern al

,
.
,
.

dimension Of mu ffle 1 9 in long in ,

.
, .

wide in high The flue a re a should

,
. .

be from one si th to o e eighth of the

- x n -

gr a te a re a The flue is best pl a ced for .

w a rd Of a line through the center Of t h e

m uffles to g et the full sweep Of the fl a me
a round th em a lthough this a rr a nge ,

FI G l — T WO M P M 1 °0 3 a
o
'
F
ment with poor dr a ft is a pt to c a use
P p ti
er s w
ec ve VI e
,

s m oky muffles
.

The w al ls Of the furn a ce a r e thick ( 13 in ) t o p revent r a di a tion . .

The front Of the furn a ce a bove the mu ffle is a rched The a rch .

tiling h a s in it a duct le a ding to the flue to c a rry o ff le a d fumes

, , .

The mu ffles a r e supported by t wo sets Of tiles pl a ced into th e

d
,

side w a lls a n someti m es by a n a dditi o n al set in the re a r end

w a ll Th ese tiles frequently pro ve w ea k a n in f a lling a w a y
.
,
d
le a ve the mu ffle without supp o rt c a using it to be short lived ,
.

The supp o rts a r e best m a de in such sh a p e of two pieces th a t

d
, ,

they will j oin under the center line Of the mu ffle a n a rch over ,

supporting e a ch other The writer h a s used supp o rts Of this

d
.

type which were perfectly s a tisf a ct o ry a n incre a sed the life

,

o f the m u ffies gre a tly A fu r na ce of the kind described h as a

.

c a p a city Of 25 to 3 0 fusi o ns (20 gr a m crucible) per h o ur including

-
,

the necess a ry cupell a tions If the fusions a r e m a de i n 30 gra m

.
-
 A SS AY F UR N ACES A ND TOO LS 3

crucibles or in in scor ifier s the c a p a city is from 20 to 24

- .
, .

With goo d dr a ft this fu r n a ce burns from 3 7 t o 4 7 lb of co al

, .

per h our which a t

, p er t o n m a kes the cost per a ss a y for
,

fuel a mount to from cents to cent when a ss a ying con

d
,

t inu o u sl y a n somewh a t more when the furna c e is no t ch a rged

t o its m a ximum c a p a cit y With a good gr a de Of co a l (6500
.

FI G . 2.
— M U FFLE F UR
T W O- N A CE Cross-sec ti on .

t o 75 00 c a l o r ies) a m a ximum temper a ture Of 1 1 50 to 1 200

,
° °

C c a n be Obt a in ed in this furn a c e a ft er 4 h o urs firing Figs 4

d
. . .

an 5 S h o w a thr ee m u ffle furn a ce Of simil a r type

- .

Co a l furn a ces m a y a lso be re a dil y m o dified t o burn crud e Oil

d
.

This ca n be d o ne by pl a cing t iling in the fir e box a n m a king

d
-
,

the necess a ry p ipe a n burner c o nnecti o ns 1

.

C udOil f Fi A
“ C l S i S VI I 3 41
F C B wm n
. . o a , r ying
e P or re ssa , r oc . o o . c oc .
, , .
4 A M A N UAL OF FI RE ASSAYIN G

F ig 6 shows such a furn a ce The burner is a i in pipe

. . .

c o nnected by a T to the oil line a lso a } in pipe A i in ,

a
. . .

ste a m pipe p a sse s into the burner pipe a t the re a r thro ugh a
p a cking nut which permits of th e a dj ustment Of the dist a nce
between the nozzle Of the burner p i p e a n the no zzle Of the ste a m d
pipe By v a rying this dist a nce the flo w o f Oil m a y be a ff ected
.

FI G . 3.
— T w o- M U FFL F UR
E N A CE . Lo ng it u d ina l sec tion
.

d
indep endent o f t h e s te a m a n o il inl et v a lv es The n o zzle of
d
.

the burner pip e is a n i in h ol e a n t h a t Of t h e s t ea m pip e a n

.

in h ol e
. .

The gr a te b a rs in th e fu r n a ce a r e c o vered with fire brick a s

sh o wn in the illustra ti o n The pl a cing o f the fire brick is Of
.

imp o r t a n c e a s the succ ess ful w o rking Of t h e furn a ce is depend ent

up o n t heir p o siti o n .

In st a rting t h e fire a piece of o iled w a st e is light ed in the fire

b o x j ust b a c k Of the burner Wh en the w a st e is burning w ell
d d
.
,

Oil a n ste a m a r e turn ed o n simul t a neo usly T h e o il a n st ea m .

v al ves a r e th en set t o give th e pro per flo w Pl enty o f w a ste .

should be used t o furnish a bl a ze until the fire b o x is hot eno ugh

 ASSAY F URN ACES A ND TOO LS

ignite the oil otherwise expl o si o ns a r e a pt to occur The

d d
to ,
.

ste a m used should b e r y a n t o insure this t h e ste a m pipe

,

l ea ding to the burn er m a y be p a ssed a ro und the flue a s shown

in the figure The v a lve D V a t the end of the ste a m line is
.

kept slightly o p en during w o rking t o permit the esc a p e o f wa ter

Of c o ndens a ti o n A sm a ll ste a m c o il m a y a lso be pl a ced in the
.

o il t a nk to k eep the Oil more fluid The furn a ce m a y be he a ted

d
.

t o a r e he a t 1 5 to 20 minutes a fter st a rting The furn a ce h a s .

a c a p a city of 25 to 3 0 a ss a ys including cupell a tions in H t o 2

,

FI G 4 — TH R E E -M U F F LE F URN A CE . Cr oss-sec t ion .

d
.

h o urs a n 50 to 6 0 a ss a ys in 3 h ours The a mount Of Oil used .

v a ri es from to g a ls p er h o u r With o il a t 8 } cents per

. .

l h
d
g a . t e c o st p er a ss a y f o r fuel is cents to cents F igs . .

7 a n 8 S h o w a wood burning m u ffle furn a ce In some districts

d
- - .

wood is the o nl y a v a il a ble che a p fuel If the fir e box a n fire - .

sp a c es a r e properly designed o f l a rger size th a n in the

d
co al furn a ce) a n a deep bed Of fuel is provided fo r the
dist nce from the g t surf ce to the bottom Of the fir e door
a r a e a -

is from 8 to 1 0 su ffici ent t emper a ture fo r ordin a ry ass a ying

ca n be a tt a ined in this type of furn a ce A l m o st a ny wood ma y .

be used .
6 A M A N UAL OF FI RE ASSAYI N G .

In the furn a ce sh o wn in Figs 7 a n 8 the gra te is 18 in d

d
. .
,

d
wide a n 26 in long ; the dist a nce fro m the gra te b a rs t o th e
.

bottom of the muffle is 26 in a n the fire sp a ce is

d
in wid e . .

d
a t the sides a n in a t the t op Fig 9 shows a wood burning . . .

furn a ce of somewh a t iflerent const ruction

' ‘
With p i no n pine .

or fir wood a t p er c o rd the cost of fuel is 6 5 cents for a ,

d a ily run Of 3 0 to 4 0 a ss a ys With a poor gr a d e Of wood a t .

FI G 5 — . TH REE M U FFL F UR
- E - NA C E Lo ng i tu d ina l S ec tio n .

per cord in a nother inst a nce 3 0 a ss a ys cost 93 c ents o r

, , ,

cents p er a ss a y including cup ell a tions

d
.
,

Coke a n a nthr a cite mu ffle furn a ces when used a r e usu a lly
d
-

sm a ller a lthough l a rge furn a ces m a y be speci a lly designed a n

,

built Of the general typ e Of the co al furn a ces describ ed .

Fig 1 0 shows a sm a ll c o ke or a nthr a cite furn a ce The fuel

d
. .

is fed in a t the t o p a n kep t well he a p ed a ro und the mu ffle A .

furn a ce of the kind sh o wn in Fig 1 0 will consume from 3 2 to 3 8 .

lb of coke per hour a cc o rding t o dr a ft With a mu ffle l 1 x 16

.
,
.

x 7 in 1 0 a ss a ys p er hour including cupell a ti o n ca n be m a de

.
, , ,

1 E . H Nu tter
.
, M in . an d S ci Pr ess,
. XCII , 3 29 , an d
Lo u is Ja nin, Jr .
, E ng an d
M
in . J
oa n ,

LXXI V . 8 10 .
 ASSAY F URN ACES A ND TOO LS

Unio n

FI G : 6.
— OI L-D U RN N G FUR N E
I AC . Cross-
sec tion
.
8 A M A N UAL OF FI RE ASSAYIN G

at a cost Of cents p er a ss a y with coke a t $ 1 0 p er t o n Ch a r .

co al ma y be used in this furn a ce in p l a ce Of coke

d
.

Fire cl a y mu ffles fo r furn a ces a r e m a de in v a rying sizes a n

-

sh a pes The best S h a p e fo r genera l use is o ne Of nea rly rect

.

a ngul a r cross secti o n with but a slightly a rched t o p The la r

d
-
.
,

gest mu ffles ordin a rily used a r e 1 9 in l o ng in wid e a n .

,
.

in high (outside dim ensi o ns) Muffles 1 9 in long 1 2 in

d
. . . .
,

wide a n 7 75 in high a r e very common in c o a l furn a ces The

. . .

mu ffles h a ve two h oles in t h e r ea r end t o induce a n a ir dr a ft

thro ugh them .

FI G . 7 .
— WOO -
D R U R NIN G M FF L F UR
- U E- N A CE Cr oss-sec tion .

The meth o d of support o f th e m u ffle in t h e furn a ce h a s gre a t

be a ring on the life Of t h e m uffle Mu ffles in a dequ a tely sup
d
.

d
p o rted soon cr a c k a n f a ll t o pi eces I t is p er h a ps b et ter to .

sup p o rt mu ffl es by one subst a nti a l r a th er b r o a supp o r t ne a r

d d
the mid le a n a cro ss t h e wh ole b o tto m a n by rest ing the d
d d
,

f r o nt end o n the furn a ce w a ll a n th e rea r en o n t w o r epl a c a ble

cl a y supp o rts t h a n t o h a ve m o re num ero us supp o rts ex t ending
,

sh o rt dist a n ces o nly beyo nd t h e w a lls o n t h e b otto m Mu ffles .

sh o uld be sto red in a dry w a rm pl a ce t o prev ent their a bs o rbing

d
m o isture a n wh en new mu ffles a r e p l a c ed in a furn a c e,it sh o uld
be fired lightly with wo o d chips fo r a n h o ur t o a nne a l t h e mu ffles ,
10 A MA N UAL OF FI RE ASSAYIN G

d
d
Figs 1 1 a n 12 represent a combina tion Of cru cible pot furn a ce
.

d d
an mu m e furna ce such a s is used in E ngl a nd The fu rn a ce
, .

ma y be b uilt Of or in a ry fire brick a n is dimensioned in such a

m a nner as to a void cutting b rick a s much a s possible It is .

fired by ca ke The two crucible furn a ces S connect with th e

.

m a in flue 9 x 9 in in size by the flues N The crucible furna c e

,
.
, .

ne a rest the mu ffle a lso connects with the mu ffle furn a ce by the
e x tr a flue 0 By these me a ns the hot g a ses Of combustion ma y
.

FI G . 9.
— W OO D -H
U R N IN G M U FF L F UR
E -
NA CE .

d
be diverted to the mu ffle furn a ce inste a d o f directly to the st a ck ,
.

The pot furna ces a r e l 4 x 14 in in secti o n a n on a ccount Of

d
.
,

the sl o ping t o p a r e 1 7 in deep a t the front a n 23 in a t the

,
. .

b a ck The t o p Of the furn a ce is best m a de of a sheet steel pl a te

d
.

cut a s require The d o o rs a r e m a d e Of t w o til es e a ch 20 x 1 0

.
,

X 4 in held together by t w o pi eces Of

.
,
in ch a nnel iron cl a mped .

by t w o in ro ds T O t h e ends Of these rods four 3 in iro n

. .
,
.

whe els a r e f a stened o n which the do o rs run The tiles a r e .

secured in the fra me in such a m a nner th a t there is a cle a r a nc e

 A SS AY F UR N ACES A ND TOO LS 11

of in a b ove t h e f urn a ce to p to freely move the doors

. E a ch .

furn a c e h as 8 gr a te b a rs of 1 in squ a re wrought iro n resting a t .

the ends on t w o simil a r b a rs pl a ced on the brickwork The ,

.

d
b a rs a r e 14 in long except the t w o center ones which a r e 18 in
. .

long a n m a y be withdr a wn through the openi ng G for dum p ing

,

t h e fire.

There a re four mufl es H in th e furn a ce 1 5 X 9

d
, in outside , .

me a surements The lower mu ffle a n p erh a p s the next upper

d
.

one m a y b e used for scorifica tion a n cup ell a tion The other .

t w o mu ffles will not he a t to a high enough tem p er a t ure for a ny

d
thing excep t a nne a ling a n ro a sting The mu ffles rest a t the .

FI G . 10.
— M UF F LE F
- U R N A CE F OR B UR
N IN G COR E .

d
b a ck a n sides on the ends of bricks cut to a level a s shown a n d
proj ecting from the furna ce body A t the front they lie flush .

on in a ngle irons A
. .

The furn a ce is built with the front entirely o p en ; the gr a te

b a rs a re the s a me as described for the crucible furn a ce When .

the muffles h a ve been pl a ced in position the sp a ce a round the

front of the mu fl es is filled with a mixture of fire cl a y a n silic a te d
of sod a t o a depth of 3 in A strong solution of silic a te of sod a
.

”
or w a ter gl a ss is mixed with 3 times its weight of w a ter until
homogeneous This solution is then mixed with fire cl a y to a
.

st ifl p a ste ; usu a ll y 1 p a rt of s o lution is required for 7 p a rts Of

’

fire cl y The mixture usu all y contra cts o n he a tin g a n shrinks

a .

a w a y a t the edges
d
These cra cks then h a ve to be fill ed a g a in
.
.
12 A M A N UAL OF FI RE ASSAYIN G

The to p of the mu ffle fu r n a ce is c o vered with tile l a id in in .

a ngle iro ns A
’
The flue V fro m t h e mu ffle furn a ce into the
.

st a ck is 1 2 x 3 in in size T h e dr a ft Of the furn a c es is c o ntrolled

. .

by pl a cing sheet iron pl a tes in front of the a sh pit d oo rs .

d
En E leva t io n
FI G . 11 — . CO M BIN A TI ON M U FF L AND POT UR N
- E -F A CE .

d
Long itu ina l S ection .

T h r ou g h P-Q d
X
an -Y .

FI G . 12 — CO
. M HI N A T I O N - M U FF L A ND PO T F U
E -
E
R NA C .

G d F urn a ces Of this type a r e in com

d
a s e e fir e
—
ol n - Fu r na ces
m o n u se a n fo r sm a ll Offic es wh ere t h e pressure Of wo rk is
d
, ,

no t grea t th ey a ff o r d a c o nv enient a n che a p m ethod Of o per a tion

,
.
 ASSAY F UR N ACES A ND TOO LS 13

G a s o len e, cc o unt Of ea se o f tr a nsp o rt a tio n a n gre a t c a l o rific

on a d
power is a lso empl o yed in o ut Of the w a y districts fo r e x tensive
,
- - -

d a ily w o rk Where c o a l is rea s o n a bly ch ea p no t a b o ve

.
,

per ton g a s olene a t 3 0 cents per g al c a nno t compete wi th it in

,
.

FI G 13 .
—G A S O LE N E F UR N A CE A PP R T U
A A S .

l a rge O ffices o r sch o ols where t h e a ss a y furn a ces a r e o per a ted

d
,

c o ntinu o usly fo r the grea ter p a rt o f t h e a y .

Fig 1 3 shows a g a solene furn a ce a pp a r a tus The furn a ce

d
,
. .

divid ed into crucible a n m u file c o mp a rtm ents is m a de Of fir e

‘

d
,

cl a y tiling b o und with Sheet iro n It is h ea ted by a br a ss a n

,
.

c o pper burner pro vided with a gener a ting d evice T h e burners

,
.

FI G . 1 4 — T HE
. C RY G O L E B URN R
A AS EN E .

a re m a de in v a rying siz es t o sui t di ff erent furn a ces The g a so .

l ene is st o red in a s t eel t a nk Of 5 o r 1 0 g a l c a p a city pro vid ed

,
.
,

wi t h a n air pu m p t o fu r nish p r essu r e A pressure g a uge is a t

d
.

t a c he t o t h e t a nk G en er a lly in pipi ng j o ins

d d
. to ,
-
.

the t a nk a n th e bu r ne r T h e burner a n piping a r e c o nnected

.
14 A MA N UAL OF FI RE ASSAYIN G

by speci a l univers a l j oint so th a t the burner ca n be swung into

d
a ,

an o u t of p o siti o n The burner (if the Ca ry) sho uld fit tightly

.

a g a inst the fir e cl a y ri ng o r boss in th e opening of t h e furn a ce so

-
,

th a t a ll the a ir fo r the combustion of the g a solene is dr a wn in

thro ugh t h e burner tube T o insure tight j o ints glue or so a p
.
, ,

o r shell a c no t white o r red le a d must be used in the screw co n

, ,

nec tio ns The g a solene is fed to the burner under a pressure

.

Of 1 0 to 20 1h th o ugh fo r speci al purp o ses higher pressures a re

.
,

used .

FI G . 15 — GAS . OL E NE TA NK A N D PU MP APP A RA T US .

d
sh o ws a det a ile view o f the Ca ry bu r n er T h e upp er
d
Fi g . 14 .

v a lve c o ntrols the m a in g a s ol ene supply a n the l o wer o ne ,

c o ntrols t h e gener a to r The burner is he a ted by the genera to r

.
,

so th a t the g a solene issuing from the m a in needle v a lve is

d
-

v a p o rized a n in its p a ss a ge t o the furn a ce dr a ws in a ir through

d
,

t h e burner tube the m i x ture igniting a n burning a t the mouth

,

Of t h e burn er in the h o t furn a ce Burners a r e listed by the di a m .

et er Of their tubes F ive sizes a r e m a de from

. to in ,
.
,

e a ch size v a rying by in .
 ASSAY F URN ACES A ND TOO LS 15

Fig . sh ows the t a nk a n pump a pp a r a tus It is best to

15 d .

pl a ce th i s a t a consider a ble dist a nc e fro m the furn a ce in o rder ,

t o a v o id a ccident a l e x pl o sions Fig : 16 sh o ws a crucible furn a c e

d
.
,

an Fig 1 7 a l a rge g a s olene mu m s furn a ce The writer h as

.
- .

a tt a ined a te m per a ture Of 1 3 50 C in sm a ll g a sol en e furn a ces

d
°
,
.

such a s Fig 16 r epres ents a n 1 250 C in l a rge furn ac es as

.
,
°
.
,

represented by Fig 17 By a speci a l constructi o n o f furn a ce

d
. .
,

with gr a phite mu ffle a n he a vy insul a tion a g a inst r a di a tion ,

with go od dr a ft the writer h a s a tt a ined (fo r m et a llurgic al ex peri

,

ment a tion) temper a tures Of 1 500 t o 1 530 C a fter three hours ° °

.
, ,

FI G . 16 —. GA S O LE NE-E UR NIN G CRUCI LE FUR B N A CE .

wi t h a 2 in g a s olene burner a s sh o wn in F ig 1 4 with g a sol ene a t a

d
- . .
,

pressure of 5 5 lb a n a consumpti o n of .
g a l p e r hour A . .

2 in Ca ry burner under 1 0 lb pressu r e will c o nsume from

- .
,
.
,

to g a l per hour A
. N O 3 1 Ca ry c o mbin a ti
. o n furn a ce .
,

d
h olding a t a ch a rge in the crucibl c o mp a rtment six 20 gr a m
e -

crucibles a n h a ving a mu m s in in size h a s a .

,

c a p a city Of 1 0 fusi o ns per h o ur including cupell a tion With ,

.

ga solene a t 3 0 cents per g a llon the c o st Of fuel per a ss a y is ,

cents .

Fig 1 8 sh o ws the Ca se burner for g a so lene o r si m il a r distill a te

. .

When in the prop er p o sition it is inv ert ed i e t h e prehe a ting , . .

,

system i s a t the top inste a d o f a t the b o ttom a s in the Ca ry

16 A M A N UAL OF FI RE ASSAYIN G

burner T h e gener a t o r o r b o ss in whi ch th e g a solene is v a por

d
.

ize is c a st in o ne pie ce with t h e mix ing cha mber whi ch is in the

d
fo rm Of a trunc a t ed c o ne a n ver y mu ch sh o rt er th a n in o ther
g a s ol ene burners The burner is sm a ller a n m o re com p a ct
. d
th a n the o rdin a ry burner Of t h e s a m e c a p a city The f a c t .

th a t it is inverted p ermits t h e g a s fo rmed fro m the g asolene

FIG . 17 — G
.
'
AS OL
E N E -B UR N IN G M U FFL F UR
E- N A CE .

in the gener a t o r t o p a s s f r eely upw a r d t o the v a lves The .

v a lves a r e Of sp eci a l d esi g n Or din a r i ly t h e n eed le v a lve

.

is used in burners o f this type th a t is a p o int ed h a r d steel

, ,

needl e wo rks in the ci r cul a r v a lve orifi ce m a king a n a nnul a r ,

op ening fo r t h e esc a pe Of t h e g a s Thi s a nnul a r o p ening v a ri es

d d
.

in di m ensi o ns a c c o r ing to t h e p o siti o n o f t h e ne edl e a n m a y ,

be cl o s ed c o mpl et ely by screwing the needl e up a s f a r a s it will

18 A M A N UAL OF F I RE A SS AY IN G

The fire cl a y bl o cks o r mu ffle he a ters m a y be re a dily re

pl a c ed by new o nes when nec ess a ry .

— Where mu ni cip a l illumin a ting g as or oth er

d d
G a s Fur na ces .

g a seo us fuel is a v a il a ble g a s fir e furn a ces a r e convenient a n

,
-

che a p Of o p er a ti o n The R eichh elm furn a ce ( A meric a n G a s

.

F urn a ce Co mp a ny) is frequently used The furn a ces require .

a ir a t lo w p ressure which is mixed w ith g a s in proper pro p o rti o n

,

before it enters the furn a ce through the sever al burners T h e .

FI G . 19 .
— CAS E G A S -B UR RNE , A IR F UR N I S HE D R Y Lo w P R ESS UR B LO W R
E E .

pro porti o n Of g a s t o a ir is c o ntrolled by v a lv es Fig 2 1 sh o ws

d
. .

t h e furn a ce G a s furn a c es p ermit Of close control of he a t a n a r e

.

desir a ble for a ccur a te t empera ture work .

FU R NA C E T OO LS —
Co nvenient t o ols a r e necess a ry fo r the h a nd
d
.

ling Oi crucibles sco rifier s a n cup els The fe a tures ess enti a l
, .

d
in these to ols a r e th a t they be light gr a sp the crucible etc , ,
.
,

firmly with no d a nger of tipping a n t a ke up little roo m in t h e

, ,

d
furn a ce A s a n illustr a ti o n of a t ool d eficient in th ese qu a lities
.

an therefo re und esir a ble Fig 22 is given This sh o ws a p a ir ,

. .

of crucible to ngs designed t o gra sp the b o dy of the crucible It

d
.

c a nno t be h a n led in a mu ffle full of crucibles owing t o t h e sp a c e ,

d
it t a kes u p in opening Fig 23 shows a p a ir of cr ucible tongs to
. .

gr a sp the sid es Of t h e crucible a n o p er a ting in little sp a ce ,

.
 A SS AY F UR N AC E S A ND TOO LS 19

d
Fi g 24 . shows two typ es of cupel tongs Fig 25 shows a g o od . .

fo rm of sco rifier t o ngs a n Fig 26 a nother form ,

. .

F or l a rge O ffices where much work must be q u ickly a cco m

p lish e dspeci
,
al forms o f t o ols m a y be u sed F igs 2 7 a n 2 8 . . d
S how a m ultiple tongs fo r scorifi Thi s a p p a ra tus will h a ndle
‘
er s .

25 sc or ifier s pr a ctic a ll y a m u m
,
eful a t one time It is composed .

Of quintuple t o ngs c o rresponding to the five l o ngitudin a l rows

,

of scor ifi er s in the mu ffle The lower p a rt of e a ch p ai r of the

d
.

tongs c o nsists Of a fork on wh i c h the sco rifier s rest a n one Of ,

FI G . 20 — M . U FFLE F UR
- N A CE WI TH SPE CIA L S U PPO RTS .

d
whose pron g s is rectiline a rly extended through t w o be a rings i n a
fr a me a n held in p ositi o n by c oll a r s This extension is free t o
d
.

revolve on the be a rings a n it is t h e a xis of ro t a tion of the tongs

, .

T o e a ch Of th em is a tt a ched a t a right a ngle a lever extending

d
, ,

upw a rd a t an a ll the l evers a r e connected by slotted j oints

t o a cross rod
-
Therefo re if by me a ns of a cra nk f a stened to
.
,

d
the end of o ne o f the extended pro ngs o ne of the f o rks is turned ,

an the scorifier s tilted to the desired a ngle the others rot a te to ,

the s a me e x tent The center of gra vity Of the sco rifiers li es to

.

dd
K Appli W k L y AI M
d
1 E w ar eller , La b o r -S a vi ng a nc es in th e or s a bo r a to r . in T ra ns
. . . .

E XXX V I , 3, an B ut 4 4 , 63 3 . A
. ug , 1 9 10 .
20 A M A N UAL OF F I RE ASSAYIN G

o ne ,
d
side of the ro t a ti o n p o int a n th ey w o uld th erefore o n bein g , ,

lifted til t in th a t direc t i o n ; this h o wever is prev ented by the

d
, , ,

cro ss b a r resting a g a inst a p o st a t th a t en Of the f r a m e t o w a rd

-

which the inclin a ti o n t ends T h e sco r ifier s a r e clutch ed by t h e

.

upper prongs of the t o ngs which is f a stened t o a spring on a p o st

d
,

Of the f o rk bel o w a n which is free t o m o ve in a vertic a l pl a n e

d
, ,

the piv o t a l p oint lying over the spring a n p o st By bringing .

FI G . 21 .
— G A s -D U R N I N G MU FF L F UR
E- N A CE .

pressure o n t h e ex t ended ends Of th ese clu t c h b a rs b ehind the

piv o t th eir other end will r is e a b o ve the sc o rifier s a n thus
, ,
d
rele a se them or permit t h e p l a cing Of th em o nt o t h e t o ngs The
,
.

pressure e x erted o n t h e rea r end s Of t h e clutch es is a cc o mplish ed

by m ea ns Of a c ro ss b a r f a sten ed t o a spring b a r which is itself
-
,

f a stened t o the h a ndl e o f t h e inst r um ent A n o r din a ry m o ld .

with 20 holes a rr a nged t o receive the c o nt ents Of t h e sco r ifier s

, ,

goes with the tongs .

 ASSAY F UR N ACE S A ND TOO LS 21

Fig 29. shows device to ch a rge 3 0 cupels a t one time It

a .

comprises a t o p sliding pl a te with o pe ni ngs c o rresp o nding ex

a c tly to the p o siti o n Of the cupels The o penings in the l o w er .

pl a te corresp o nd with th o se Of the up p er o ne ; the pl a te how ,

ever rests o n t wo a dj a ce nt sides e x tended d o wnw a rd a t right

d
,

a ngl es to the pl a t e a n to e a ch other thus fo rming t w o cl o sed

d
,

sides Of the inst r um ent ; o ne a t the fr o nt a n the oth er a t the

FI G . 22 .
—CR U CI HLE TO G
N S . Undi es r a b le mo d
el .

FI G . 2 3 — CR U CI R LE
. TO G N S .

FI G . 24 — C . UP E L TO G
N S .

FI G 25 .
— S CO RI F E R TO
I N GS .

FI G . 26 .
— S CO RI F R TO
IE N GS .

right h a nd sid e The height Of t h ese sid es is such th a t when rest

- .

ing on t h e b o tt o m Of t h e mu ffle t h e b o t t o m pl a te will be so m e dis

d
t a nce a bov e t h e cupels a n by a slight p ul l fo rw a rd a n a p ush
,
d
t o the left with the h a ndle Of the instru ment the set o f cupels
will be pe r fec tly a lined in b o t h direc ti o ns a n t h e a pertures in d
the l o wer pl a t e will ex a c tly c o ver th e t o ps Of the cup els The .

le a d bu t tons a r e pl a ced in the a pertures Of the upp er pl a t e

 A M A N UAL OF FI RE ASSAYI N G

FI G . 27 — . M U LT P L
I E SC O R F R TO G
I IE N S . ( K el ler

FI G . 2 3 — M U L r I P LE
. S O R F R TO G
C I IE N S . ( K ell er .

FIG . 29 C U PS“(h
— . . A BG l N G DEV ICE . ( Kellen)
 AS S AY F UR N ACES A ND TOO LS 23

d
d
anrest on the l o wer pl a te before i ntroducing the instrument into
the furn a ce a n wh en it is pl a ced Over th e cupels which h a ve
, ,

b een properly a lined in the mu fie the upper pl a te is pushed ,

FI G . 30 — . PO UR N GI M OL DS .

f o rw a rd to a sto p point bringing the a p ertures Of the t w o pl a tes

-
,

into register th us c a using t h e le a d buttons t o dro p d o wn into

,

the cup els The h a ndl e Of the upper pl a te ru ns thro ugh guid es
.

FI G . 31 — C UP E L TR A Y .

d
fixed to the h a n le of the lower p l a te ; both h a ndles a r e c o nnected
wi t h a spring which a cts a s a br a ke wh en the upp er pl a te is
,

push ed fo rw a rd to dro p the buttons a n a lso serv es t o bring it ,

d

FI G . 3 2
.
— FR I E -C A L Y A NNE A LI N G -C U P TR
A Y .

b a ck into its origin a l p o sition in which t h e buttons c a nn o t drop

,

t h ro ugh the a p ertu r es in the l o wer pl a te

d
.

M ol s — Fig 3 sh o ws m a chined c a st iro n molds to receive

0 .
-
24 A M A N UAL OF FI RE ASSAYIN G

the molten fusions The sh a rp c o ne sh a ped m old is prefera ble

.
-

d
to the sh a llow hemisph eri c a l type a s the l ea d buttons a re th en
d
,

sh a rp a n well defined a n sep a r a te ea sily fro m the sl a g The .

m old is best m a de with a screw h a ndle so a s t o be ea sily rep a ired

-
,

d
in c a se of bre a k a ge The inner surf a ce of the m o lds S ho ul d be
.

m a c hined smooth to permit the re a dy s ep a ra ti o n o f sl a g a n

,

le a d butto n fro m the m old Fo r sco rifica t io n fusi o ns sm a ller .

,

m olds a re Often used .

FI G 33 .
— FR I E -C LA Y CR U CI HLE S

the tr a nsf er Of cup els to t h e p a r ting roo m iro n cupel tra ys

d
Fo r , ,

a s illustr a ted in Fig 3 1 a r e us ed . The h a ndl e is rem o v a bl e a n

,
.
,

o ne h a ndle s er v es f o r a nu m b er o f t r a ys Fo r t h e a nn ea ling o f .

gold be a ds o r co r nets fir e cl a y t r a ys a s sh o wn in Fig 3 2 a r e

d
- .
, ,

employed Fire cl a y h o wev er is v er y ea sily bro ken a n m o re

d
.
-
, , ,

s a tisf a cto ry tra ys a r e m a d e Of sheet iro n a n h ea vy a sbesto s

b o a rd .

C U C I B L S AND S CO R IFI E R S Fi r e—cl a y cru cibles a r e l a rgely

R —

d
E .

us ed in th e U nited S t a tes a n fir e cl a y w a r e fo r a ss a y purposes is

,
-

m a d e to a l a r ge ex t ent in s o m e Of the west er n S t a t es Foll o wing .

is the a n a lysis Of a Col o ra d o c r u cible cl a y : 1

E dO. r to n, A ssa y Cr ucib les T h eir Cla ys

. . T ra ns . A m Cer a mic S oc
. .
, X ,
26 A M A N UAL OF FI RE ASSAYIN G

poorer gr a de Of domesti c goods which a re som e times sold The .

d
highest gr a de of domestic m a teri a l is however in most c a ses t o , ,

d
be preferred a s being fully a s long lived a n che a per .

The speci al mixture of cl a ys a n th eir tre a tment fo r c r ucibl e

m a n uf a cture is gener a lly a tra de secret j e a lously gu a rded a n , d
little i nf orm a tion c o ncerning the subj ect is a v a il a ble
d
.

S co rifiers a r e m a de Of the s a me cl a ys a s the crucibles a n a r e

design a ted in size by their o utsi e di a meters ; 2 an d d
-in sizes a r e m a de These will h o ld a vol u me of 1 5 c c
. . .
,
.

FI c 36 — BU CK B O RD B RU
A SH E S

d
. . .

c c 3 7 c c a n 1 00 c c respectively The
. .
,
. . in sco r ifier is
. .
,
.
-
.

the o ne comm o nl y used Fig 34 sh o ws the ordin a ry typ e o f . .

sco r ifier s R o a sting dishes a r e sh a ll o w fir e cl a y dish es Simil a r

.
-

t o sco r ifier s but not so thick They a r e r a ted by th en di a m et ers ;

d
.
,

the comm o n siz es being 4 5 a n 6 in Fig 3 5 S h o ws the or

d d d
. .
,

ina r y buck b o a rd a n muller a n Fig 3 6 buck bo a rd bru shes

d
. .
,

Fo r the descripti o n Of oth er min o r t oo ls a n a pp a r a tus a s screens

d d
, ,

pliers a n c r ushing a n grinding m a chinery nec ess a ry to t h e

,

a ss a y l a bor a tory t h e re a der is referred t o the v o lumin o us a n

,
,

d
well illustra ted c a t alo gues Of the a ss a y supply h o uses Ba l a nc es
- .
,

weights s a mpling t ools cup els p a rting d ev ices etc a r e dis

, , , ,
.
,

cussed in their res p ective ch a p ters .

 CHAPT E R II

D EFI N I T I ONS ; R E A G E NTS ; T HE A SS A Y OF

R E A G E NTS

A ssa ying includes al l th ose oper a ti ons of a n al ytic a l chemistry

d
which h a ve for their obj ect the de t ermin a tion o f the constituents
of o res a n met allurgi c p roducts Three meth o ds a re used : .

d
( )
1 F ire ass a ying ( dr y methods ) ; ( 2) gr a v i met r ic a n a lysis ( wet
meth ods) (3) volumetric a n color imetri c a n al ysis (w et methods) .

Thi s wor k tre a ts of fir e ass a ying o nl y with a few exce p tions ,

.

The qu a ntit a tive determin a tion Of the foll owing m et als is dis

d
cussed : gold silver p l a tinum , etc le a d a ntim o ny bismuth tin
d
,
.
, , , , ,

an mercury ; chiefly however gold a n silver , , .

d
Fire ass a ying comp ri ses the sep a ra tion of the met a l sought

d
from th e other com p onents of the ore by he a t a n suit a ble ,

fluxes an then the wei ghi ng Of it in a st a te Of gre a ter or lesser

,

dd d
purity .

—
G ol a n S ilvan G old a n silver a re deter mi ned i n their
.

o res,
or met a llurgic p rod u cts by c ollecting them wi th le a d
, ,

fo rming a n a lloy which ma y be a ccom plish ed either by the

,

crucible or the sco rifica tion fusion the le a d being then driven Off
d d
,

by cup ell a tion a n the result a nt be a d of the gold a n silver

,

d
a lloy weighed The sep a ra ti o n of gold from silver is a ecom
.

p lish e by p a rting in most inst a nces with nitric a cid r a rely by ,

sulphuric a cid .

In order t o successfully coll ect the p recious met a ls by me a ns

o f le a d it is essen t i a l th a t the o r e be mixed wi th suit a ble flux es
, ,

d
so th a t in fusion the ore is thoro ughly decomp o sed chemic a lly ,

a liquid sl a g o f the p roper c o nstitution p roduc ed en a bli ng

d
an
,

the le a d with it s a ll o yed gold a n silver to settle from the sl a g

by gra vi ty thus a ff ording a re a dy sepa r a tion
, .

27
28 A M A N UAL OF FI RE ASSAYI N G

TA B LE I .
— R E A G E NT S C OMM ONLY USE D I N ASS A YING

N a me Fo r m u l a N a t ur e (c hem i ca l)

Lit ha r ge Pb O
S o di u m c a r b o na te . N a , CO,
S o diu m bic a r bo na te . Na HCO,
Pota ssiu m ca r bo na te . K , CO,
S ili ca . S iO,
Bor ax Na , B , O I OHS O
B or a x gla ss . Na 2 B , O
Fluo rspa r ‘
Ca F,
Ca O
Hema t it e FezO,
T est or gra nu la t ed lea d
S heet lea d

Cha r coa l .

Co k e du st .

Flo ur
Lea d flu x

B la c k flux su bst it u te
Po t a ssi u m cya ni e d
Pota ssi u m nit r a te .

S a lt (so di u m c h lo r id e)

Lith a r ge
is ct ed in the crucible by r edu cing a gents
d
1 . a on ,

su c h as ch a rco a l ,
et c .
,
an m et a llic l ea d p r o duc ed a s fo ll o ws :
2Pb O + C = 2Pb + 0 0 ,

The lith a r ge no t reduc ed is a cted on by silic a a n b o r a x gl a ss d

d
,

pro ducing silic a tes a n b o r a tes o f l ea d a s foll o ws ,

Ph o S io , = Pb S iO, , et c .

2
Lith a r ge
m elts a t 8 8 4 C °
.

2 3 S o dium c a rb o n a te is decomposed by he a t in the cm

,
.

cible a s f oll o ws a t high temp er a ture no t usu a lly re a ched in

, ,

a ss a ying

N a zCOs N a zO CO,
Or in t h e pres en c e Of si li c a
, , a t l o w er tem p er a tu r e ,

N a ,,CO3 S iO2 Na zS iO, CO

dm d b y te m pera tu r es d d y ing
dM
No t ec o p os e in th e c r u c ib l e or ina r ily u se in a ssa .

Mostow itsch , M eta ll ur ai e . IV . 648 . D oeltz an osto w i tsc h . M eta ll u r ai e , IV . 290

.
 T HE ASSAY OF REAGE N T S 9

T h e N a , O, wi t h silic a f o rms sodium silic a t es a s N a , S iO, et c

, , ,
.
,

d
whi ch a r e v ery fusible It a lso p o ss ess es t h e pro perty Of rea dily
d
.

f o rming sulphides a n sulph a tes a n in t h e p resence of met a llic ,

Fe Of freeing l ea d in th e ch a rge fro m sul p hur

,
.

Na zCO, m elts a t 8 1 4 C °
.

A ss a yers frequently u se s o diu m bic a r b o n a te in pl a ce Of c a l

cine d
s o di um c a rbon a te p a rticul a rly in the U nit ed S t a t es o n , ,

a ccount of its l o wer cost Thus while refined sodium c a rbon a te .

c o sts 8 cents per p o u nd sodium bic a rb o n a te costs but 3 cents ,

p er pound a t comm erci a l,

cent ers When the s a lts a r e c a l eu .

l a t ed to the b a sis Of t h e b a se ( N a zO) cont a ined the di ff erence in ,

c o st is no t so wide still t h e bic a r b o n a te is ch ea per N ev erth e

,
.

less it is prefer a ble to use the c a r b o n a t e since the gre a t a mount ,

o f g a s ev o lved in the d ec o m positi o n of the bic a rbon a te is a p t t o

c a use m ech a nic a l l o sses in the a ss a y Crude sodium c a rb o n a te .

o r s o d a a sh m a y be us ed c osting a bout 2 c ents p er pound

- In .

the cru cible under t h e influence Of h ea t t h e bic a rb o n a te d a c o m

p o s es a s foll o ws :
2Na HCOs Na ,,CO3 HzO CO2

4 P o t a ssium c a r bon a t e a cts in a simil a r m a nner to sodium

.

c a rb o n a te It m elts a t 88 5 C
d
°
. .

5 S ilic a is a p o w er ful a cid flu x a n co m bines with the met a llic

.

o x id es o r b a s es p r es ent in t h e ch a r ge t o f o rm the sl a g whic h is ,

m a i nl y comp o s ed Of silic a tes It is pres ent in m o s t o res in co n

d
.

si er a bl e qu a ntity r a nging fr o m sm a ll a m o unts in b a sic o res to

,

the m a in bulk Of t h e o r e in qu a r tz ores It m elts a t 1 7 75 C 1

.
°
.

( Qu a rtz ) —
( R Ob er t S -A ust en ,

6 7 A nhyd r o us b o ric a cid ( B 2 0 8 ) Bo r a x

d
, .
,

l OHzO) a n Bo r a x gl a ss
,
or a nhydro us sodium
b i b o r a te
- Bo ric a cid rea dily f o rms b o r a tes o n fusi o n a t co m
.
2

i l high temp r t e with lithium pot ssium s diu m

d
p a r a t v e y e a u r a o , , ,

an sil ver o x id es gener a lly fo rming o r th o b o r a tes

,

Bo ric a cid do es no t rea dily diss o lv e silic a but sodium or p o t as ,

sium met a b o r a te -
form ed pro b a bly dur
ing the fusi o n of b o r a x gl a ss o r s o dium b i b o r a te
d
-
,

with b a ses will rea dily diss olve silic a a s well a s a lu mina a n
d
, ,

c hro mic oxide T h e a lk a lin e met a b o r a tes a r e m a rke ly vol a til e

d
.
-

wh en m o lten a n deliqu esce in the a ir .

1D a y a n S h ep a r d d g i v e th e m el ting p
- o int of S iOz a t a ppr oxi m a tely 1 625 °
C J ou r . Am .

Chem S oc , XX VIII
d
. .
, 1 096 .

2
W . G uer t ler . S pr ech saa l , X LV , 6 1 2 ; f ou r . S oc Chem In
. . .
, Feb 25 . 1 9 08 . 1 58
. .
 0 A MA N UAL OF F I R E A SS AYIN G

Bor a tes a re cl sifiedas as foll o w s : Ort h O-bor a tes , e .

g 3 C
.a O B , O,;
.

b r te qui bor te
d
-
se s -
pe o a s e g , a
. . s e
, g , . .
,

met a bo ra tes
- a n bi bor a tes e g
, The -
,
. .

following bora tes a r e o f interest to the a ss a yer : Ma gnesium

ortho bora te 3 Mg O B, Oa ; m a gnesium pe bor a te
d
- - .
, ,

the corresponding bor a tes Of nickel a n cob a lt ; the orth o- pe

d d
,

met a a n bi bor a tes o f c al cium strontium a n b a rium Le a d

d
-
, .

oxide forms gl a sses wi t h bori c a cid a n b o r a x Of w hich Pb O B, O8

d
.
,

is h a rd like flint gl a ss a n m a y be soften ed in boil,

ing Oil Other subst a nces which ma y not be compounds a re

.

S Cu zO 2 B, OS ; d Bismuth ,
d
. an

ntimony a n a rseni c a lso form bor a tes

d
a .

Bor a x a n bor a x gl a ss a r e fluxes used frequently by a ss a yers .

d d
They a r e c o nsidered a cid fluxes but it will be noted from the ,

a b o ve th a t they h a ve the p ower of issolving sili c a a n a lumin a

an dwill hence corrode crucibles They c a n be u sed t o flux .

silic a to a ce r t a in extent a u se however to which they a re not , , ,

—
put S odi um bi bor a te h a s the p roperty Of p a ssing gr a du a lly
d
.

from the liquid to the solid st a te (a morphous) a n vi ce ver sa ,

under o rdin a ry conditions with no definite freezing or melti ng

p oint It c a n be m a de to cryst a llize or freeze a t a d efini te tem
.

nly under the influence f vibr t i on from r pidly

d
p e r a t u r e o O a a r e

p e a t e shocks C ryst a l l ized so dium

. b i-bor a te melts a t 7 42 C 1 °
.

The u se Of bor a x gl a ss a s a flux to form e a sily fusible bora tes

with met a llic b a ses is d ependent upon the liber a tion of boric a cid
from the bi b o r a te in the presence Of the free b a ses Wh a t p a r tic
-
,
.

ul a r bor a tes form is l a rgely a question of tem p er a ture a tt a ined .

The use of much bor a x g ives rise to h a rd stony S l a gs very tough , ,

from which the le a d button sep a r a tes with di fficulty Often a .

film of le a d will a dh er e t o the sl a g c a using mech a nic al l o ss ,

.

Sl a gs c o nt a ining much b o r a x will Often fly t o pieces suddenly ,

d
2
esp eci a lly wh en t o u ched with a sh a r p instrument while cooling
d
.
,

This is due to ev it rifica tio n o f a m o rphou s gl a ssy bor a tes a n

t h e fo rm a ti o n of definite cryst a lliz ed b o r a tes .

In flu x ing ores cont a ining zinc it is t o be n o ted th a t b oric

o x ide either a l o ne o r mi x ed with one h a lf its Weight of bor a x
,
-
,

will flux zinc oxide into a very fluid sl a g which is h o wever ,very , ,

c o rro sive to cl a y cru cibles .

d
A llen , A m J o u r S c , X X , 1 02 I
d
Da y an . . . .

E . Clennel l, E ng a n M i n J ou r , XXX
. . . L VII , 696 .
 T HE A SS AY OF REAGE N TS 1

8 . occ a sion all y used in a ss a yi ng It melts a t a

Fluo r sp a r i s .

comp a r a tively high tem p er a ture 1330 C but when fused is very ,
°
.
,

thi nl y fl ui d The gre a ter p a rt Of it rem a ins unch a nged through

d
.

o u t the fusion a n hence its lime c a nnot be considered a s a v a il

,

a ble fo r fl uxing silic a It gives the S l a gs cont aining it a sto ny.

a ppe a r a nce Owi ng t o its g re a t fluidity it h a s the p ro p erty

d
.
, ,

sh a red by so d a a n lith a rge to some ex t ent of holding in sus ,

pension unfused p a rticles thus still m a king a fl ui d sl a g Where ,

.

t h e decomposition Of the ore t o be a ss a yed is essenti a l a s it is ,

in m o st c a ses its use is not t o be a dv o c a ted

,
.

9 Lime is used either a s t he c a rbon a te o r as the o x ide o r

.

hydr a te In the crucible it is c o nverted into oxide the c a rb o n

.
,

a t e beginning to l o se its CO2 a t 8 00 C In itself it is e x trem ely °

.

infusible ( 1 9 00 C ; H empel but with silic a when j oin ed

d d
°
, ,
.

with o ther b a ses a n in m o d er a te qu a ntities it m a kes very c ,

sir a ble S l a gs It is found in m a ny o res Ma gnesi a a cts in a

. .

simil a r w a y Its mel ting point is 2250 C (Hem p el

d
- °
.
.
,

1 0 H em a tite or n a tura l ferr ic o xide a n limo ni te a r e o f

d
, ,
.
,

frequent occu r renc e in o res a n a r e s o metimes a dded a s a flu x ,

.

Ferric oxide h as a high mel t ing point a bout 1 560 C In the ,

°
.

c r ucibl e it is c o nve rt ed by reducing a gents such as a rgol ch a r

d
, ,

c o al etc t o fer r o us o xide (FeO) a n then unites with silic a to

,
.
, ,

form silic a tes T h e f a ct th a t it is reduced to ferro us o x ide co n

.
,

v er sely gi v es it a n o x idizing p o wer M a ng a n ese oxides a cting .

in a simil a r w a y a re a lso frequen t ly found in ores A l umin a

d
.
,

A 13 0 3 is Oft en f o und in ores a n

, u ni tes with silic a t o form ,

silic a t es I t h a s no o x idizing p o w er A 120 3 m el t s a t 20 1 0 C

. .
°
.

K a no l t ( 1 9 1 2 )
d
Test le a d a n sheet le a d a re used chiefly in the scor ific a
d
11 .

tion a ss a y a n in cupell a ti o n In both of these Oper a tio ns t h e .

le a d is oxidized by the oxygen of the a ir to

lith a rge In t h e scorifica tio n a ss a y p a rt Of this Pb O vol a tilizes ;
d d
.

the gre a ter p a r t becomes fl uid a n h olds in suspension a n

soluti o n other met a llic oxides derived fr o m ores thus f o rming ,

wh a t is termed a n oxide sl a g In c upell a ti o n p a rt Of the l ea d

d
'

.
,

is vol a tilized a s Pb O a n p a r t is a bsorbed by the cupel a s Ph O

,
.

Le a d melts a t 3 26 C °
.

1 2 A rgo l is a c r ude bit a rtra te Of p o t a ssium sep a r a ting out

.
,

in wine c a sks from the wine on st a nding On he a ting it bre a ks

,
.
,

up a s follows
2 KHC, H, O, he a t K, O 5 H3 0 60 0 20
32 A M A N UAL OF FI RE ASSAYIN G

T he d
c a r b o n a n c a rb o n m o n o x ide set fr ee gives it its reducing
p o wer The KzO l eft a cts a s a b a si c flux
d
. .

1 3 1 4 1 5 Ch a r c o a l c o ke c o a l dust sug a r a n
, ,
.
,
fl o ur a r e
, ,

reducing a gents by virt ue Of the c a rb o n o r hydro gen o r b o th , ,

th a t they c o nt a in .

16 Le a d flux is a re a dy p r ep a red flux used m a inly in t h e

-
'

a ss a y Of l ea d o r es for l ea d It h a s t h e fo ll o wing c o mposition :

.

S o di u m bi c a r b o na t e 1 6 p a r ts
Pota ssi u m ca r b o na t e 1 6 p a rt s
B or a x gla ss . 8 p a rt s
F lo u r 4 pa rt s
0

It is a ls o m a d e up in o th er pr o po rtions
d
.

1 7 Bl a c k flu x is m a de Of 1 p a r t KN O3 a n 3 p a rts a rgo l
d d d
.
,

It is so m etimes Used in t h e tin a n l ea d a ss a y

d
efla g r a t e . .

1 8 Bl a c k flux substitut e c o nsists o f 3 p a r ts Of fl o ur a n

.

1 0 p a rts o f N a HCOs
d
It is used in the tin a ss a y
. .

1 9 T h e a lk a lin e cy a nid es a r e p o wer ful p o iso ns a n

. wh en
p o wd ering th em fo r u se a s a flu x gr ea t c a r e must be t a ken no t to
inh a l e t h e dust T h e m o rt a r in which t h e pulv er izing is d o ne
.

sh o uld b e c o ve r ed by a cl o th during t h e o p er a t i o n which is best ,

c o nduct ed a t a n o p en wind o w T w o kinds o f c o m m er ci a l cy a nide .

m a y be rea dily pu r ch a s ed o n t h e m a rket 1 Wh a t is kno wn a s . .

“p o t a ssiu m c y a nid e ” but whi c h c o nsi sts o f h e m i x ed cy a nid es

d
, t
Of s o dium a n p o t a ssium c o nt a ining v a rying a m o unts o f im
,

pu r i t ies such a s a lk a line c a r b o n a tes sulph a t es et c T h e qu a lity , ,

.

is ex press ed by t h e cy a no gen c o nt ent in t erm s of KON Thus ,

.

“ 8 per cent K N ” is in c o m m n use With o ut going into

9 C . o .

d et a il it is t o be no t ed th a t s a lts Of this typ e m a y c o nt a in con

d d
,
“
98 p er c ent KCN
”
si er a b l e i m purity a l th o ugh r a t ed a s
,
an .
,

unl ess kn o wn t o be goo d sh o uld not be us ed in the tin a ss a y .

Pure p o t a ssium cy a nid e c p ca n be obt a ined onl y a t a co m ,

. .

p a r a t iv el y high p r i c e 2 S o dium cy a nid e This

. is.a c o m m er cia l .

s a lt th a t m a y b e Obt a ined n ea rly pure When its cy a no gen .

c ontents a r e r a t ed a t 1 25 t o 1 3 0 p er c ent KON it m a y be us ed .

,

with s a fety a s a flu x f o r t h e tin a ss a y .

“
A s a m ple Of c o m m er ci a l 98 p er c ent KON impuriti es no t
d
,
.

kn wn
o h a a freezing p o int Of 526
- C a s determin ed in the °
.
,

a uthor S l a b o r a t o ry .

Wh en h ea t ed s o m ewh a t a b o ve its melting p oint in the p resenc e

of a ir a lk a line cy a nide fo rms cy a n a t e a n th en d ec o mp o ses
, d
with the liber a ti on Of cy a no gen Cr ucibles in which it is used .
34 A MA N U AL OF F I RE ASSAY IN G

d
i n the m A s lith a rg e is al mo st i nv a ri a bly u sed in the c ru c i bl e
d
.

a ss a y ,
an test le a in th e scorifica tion assa y a ny silver o r , ,

p o ssibly g old introduced into th e resul t s by their use must be

,

Most a ss a y
d
subtr a c ted so as no t to be a sc ribed t o the ores
,
.

d
supply house s no w furnish pr a ctic a lly silver free lith a rge a n
-

d
le a d c o nt a ining only tr a ces Of silver a n no gold
d
.

The method Of determi ni ng silver a n gold in lith a rge a n

test le a d is a s follows
T he follow ing ch a r ge is w eig he d o ut in dupli ca te
3 assa y tons
S o di u m ca r bo na te 20 gra ms
S ilica
A r gol .

!b
Bora x gla ss 5 gr a ms (a s a co ver )
The v a rious ingredients put fro m the sc a le p a n o n a shee t
d
a re

d
Of gl a zed p a per a n th o roughly incorp or a ted by mixing It is .

essenti al to w eigh the lith a rge a n a rgol a s a ccur a tely a s p ossible

with the p ulp b a l a nces in use .

h
T e incorpor a ted ch a rge is then tra nsferred t o a 20 gr a m -

d
c r ucible a sh al l o w cover of b o r a x gl a ss being put on t op o f the
,

c h rge
a a,
n m
then fused in the u ffle furn a ce for from 25 t o 3 5
-

minutes a t a yell ow he a t ( 1 000 The fusion is c o nsidered

°

d d
complete when the ch a rge is in quiet fusi o n th a t is when there , ,

is no more bubbling a n boiling in the ch a rge a n when the

o nl y m otio n observ a ble is th a t due to convectio n current s The
d
.

ch a rge is then p oured into a n iro n mold a n allowed to solidify ,

which t a kes a pproxim a tely 1 0 minutes The le a d button is then

d
.

sep a r a ted fro m the sl a g by the h a mmer a n fo rmed into a c ube

d d
.

It is weighed a n its weight rec o rd ed in gr a ms a n t enths o f a

gr m in the ss a y no te book a definite a ss a y number being
d
a a -
,

a ssigned to this a ss a y a n its duplic a te The le a d button is then .

cupeled the cupel being first pl a ced in the muffle for 1 0 t o 1 2

,

minutes before the le a d butt o n is drop ped into it If t h e butt o n .

weighs from 1 5 to 20 gr a ms a s it sh o uld it will t a ke 25 or 3 0

, ,

minutes t o finish t h e cupell a ti o n th a t is to drive o ff the le a d , ,

.

The end Of this opera tion in this p a rticul a r inst a nce is denot ed
, ,

by th e d a rke ning of the sm al l silver be a d The be a d is then r e .

moved fro m the cupel a fter this h a s bec o me cold fl a ttened o n ,

a sm a ll a nvil with a bl o wpipe h a mm er cl ea ned Of a dh er ing

d
,

bone a sh from the cupel by a button brush a n weighed c a re

-
,

fully On the a ssa y b al a nce s the weig h t being recorded in milli

,
 T HE ASSAY OF R EAGE N TS 35

d
gr a ms a n hundredths of a milligr a m The weight Of the be a d .
,

divided by the number of a ss a y t o ns (3 ) t a ken in the a ss a y g ives ,

t h e number of ounces cont a ined in a t on (2000 lb ) of lith a rge or .

,

the number of milligr a ms per a ss a y t o n Of lith a rge 1

If the .

p resence of gold is sus p ected in the lith a rge the silver be a d from ,

the cupell a ti o n a fter weighing is dropped into a p a rt ing cup

, ,
-

d
filled with hot nitric a cid (9 p a rts w a ter to 1 p a r t concentr a ted
nitric a cid sp gr which will issolve the sil ver a n le a ve
,
. . d
the gold a s a bl a ck residue This re sidue is w a sh ed th ree times
d
.

by dec a nt a tion with c old distilled w a ter c a refully dried a n ,

d
a nne a led a t a red he a t in the mu ffle ; a fter cooling it is weighed

The weight of the gold is rec o rde

d
a s a lre a dy described for silver

d
.

an the n subtra cted from the weight of the origin al gold a n

silver be a d The di fference in w eight gives the a mount of silver
d
. .

To determine the S ilver a n gold in test l ea d weigh out 3

d
d
,

a ss a y tons pl a ce in a in sco r ifier a a p inch of bor a x gl a ss

d
-
,
.
, ,

scorify in the mu ffle a t a yellow he a t ( 1 000 A s the

d
°
an

le a d oxidizes t o lith a rge this melts a n forms a sl a g which , ,

d
o wing to the c o nvexity Of the meniscu s of molten le a d f a lls to ,

the side of the surf a ce a n fo rms the sl a g ring le a ving a disk o f ,

fresh le a d e x p o sed The sco rifica t io n is finished when the sl a g

.

fin a lly covers a ll the le a d The ch a rge is then poured into a n .

iron mold the further method of procedure followed being iden

,

tic a l with the one described f o r the lith a rge a ss a y

d
.

d
It is p o ssible to Obt a in t est a n sheet le a d with o nly tr a ces
Of silver a n lith a rge pr a ctic a lly free from sil ver It is Often
,
.

desir a ble th a t the lith a rge should cont a in a uniform a mount of

silver for whenever l o w gr a de gold ores deficient in silver a r e
,
-
, ,

a ss a yed silver will h a ve to be a dded a t some st a ge Of the a ss a y

,

in order t o insure p a rting or the com plete se p a r a tion of the gold ,

from the silver In a ss a ying very low-gra de gold ores in which

.
,

pr a ctic a lly only g old is present the fin a l b ea d might be so sm a ll

d
,

a s to S ink into m inut e cr a cks in the cupel a n thus be lost The .

a ddition Of S ilver in this c a se either by a dding it in the met a llic ,

st a te or by its presence in the lith a rge obvi a tes this di fficulty ,

.

Lith a rge will frequ ently cont a in fro m to mg o f .

silver p er a ss a y t o n It is h o wever not s a fe to a ssume the

.
, ,

a bove figures The test le a d ordin a rily bought from the su pp ly

.

houses cont a ins only tr a ces o f silver .

Ford d pella tion a n d f d

m d
1
a iscu ssio n of w eig h ts use in assa ying , cu w eig hi ng . r e erence sh o ul

be a e to th ese su bj ec ts .
 CHA PTE R III

S A MPL I N G

Proper s a mpling is o f the utmost i mport a nce for unless the ,

sa mple t o be a ss a yed a ccur a tely represents the lo t Of o r e or

m et al lurgic p roduct fro m whi ch it is t a ken in o th er words u nl ess , ,

it is a true s a m ple the grea t est c a re in the a ss a y its elf me a ns,

n o thing La r ge a mounts of m o ney a re invo lved in settlements

.

m a de on the a ss a y of fin al s a mpl es representing m a ny tons Of

rich or e m a t te bullions etc Mills a n sm elters purch a se ores d
d
.
, , ,

by the c a rl o a d on the a ss a y Of the fin a l s a mple a n even slight ,

e r rors me a n l o ss eith er t o the shi p p er o r the purch a ser Where .

“ ”
so c a lled
- specim en a ss a ys a r e m a de the s a m pling Of the ,

sm a ll a m o unt of pulp is usu a lly a simpl e m a tter a lthough a ccu ,

r a cy is a lso required In m o st c a ses the s a m ples representing .

,

l a rge lots a r e h a nded to the a ss a yer so th a t he is usu a lly not

, ,

directly c o ncerned a s to h o w the s a mples were Obt a ined ; but in

gener a l h e S h o uld be f a mili a r a s t o h o w s a mpling is c o nducted .

S a m pling m a y be cl a ssified under t w o he a ds

1 H a nd s a mpli ng
d
.

a Co ni ng a n qu a rt ering
. .

b A lt ern a te S h o v els
. .

S plit S hovels
di
0 . .

. R ffling .

2 . Ma chin e s a mpling :
a . P a rt of t h e o r e stre a m fo r t h e wh ol e time .

b . The whole Of the o r e stre a m p a rt Of the time .

Wh a tever the m eth o d Of s a mpling used a distinct rel a ti o n

d
,

m ust ex ist betw een t h e w eight Of t h e s a mple a n the size Of t h e

o r e p a rticl es Thus if the o r e p a r ticl es a r e l a rge ( 1 0 t o 1 2 in
.
,
.

di a met er) a l a r ge s a mp l e must be t a ken ; if the p a rticles a r e

s m a ll in ) a sm al l s a mple will if pro p erly t a ken
d
to .
, ,

a ccur a t ely r epres ent the lo t Of o re l A n Ol rule in f o rc e o n .

d
y a n Pr a c tice o f Or e S a mpli ng A I XX V
d
1 B r u nt o n, T h e T h eor , T r a ns M E . . . .
, , 8 26
an T r a ns .
, A . I . M E
. .
, X L 56 7 No te s
, . o n S a m pli ng , M i n R ep or ter , X
. LV , NOS .
—
7 16
(inclusi ve) .
 S AM P LIN G 37

G i lp i n County , Color a do , ores c a rrying from

, 1 to 4 oz gold .
,

illustr a tes this

Dia m o f la r g est p iec e, in rnch es
.

Minimum w eig h t o f sa mple , in l bs 4 32 2 56 20 48 1 63 48

The p roper weight of s a m ple for a ny desired size of ore p a rticle

is Obt a ined by multiplying the known weight for the g iven S ize
by the cube of the r a tio of the desired size to th a t of the given
S I ze .

As ex a m ple of mill pr a ctice by m a chine s a m p ling on

an

Cri p ple Creek ores o f from 2 to 6 o z go ld per t en the f o ll o wing .

,

d
is given
The ore is crushed to p a ss a -in r ing a n from the tot a l .
,

bulk a V ezin s a mpler cuts ou t one fourth This is p a ssed to - .

crushing rolls whi ch reduce it to in size It is then ele

d
- . .
,

v a t e to a nother V ezin s a m p ler which t a kes out one tenth Of the ,

-

d d
b ul k the fin a l s a m ple being o ne f o rtieth Of the o r e or
,
per cent -
,
.

This is then cut d o wn a n cru shed finer a n s a mpled in the

usu a l w a y ( a l tern a te shovels described further o n In ,
.

smelting works where it is desir a ble to h a ve the product going

,

to the furn a ces a s co a rse a s possible the a b o ve method is modi

d d
,

fie by not crushing so fine a n by t a king l a rger s a mples ; or h a nd

s a mpling is em p l o yed The size of the s a mple depends not o nly .

on the size of the ore p a rticles but a lso on the n a ture of the ,

o re . If the v a lues a r e uniformly distributed sm a ller s a mples ,

“
will do th a n a re necess a ry where they a r e spotted or ir r eg u
la rl y distributed While m a chine s a mpling with prop erly con
d
‘
.
,

structed a pp a r a tus is l a r gely in use a n is mo st d esir a bl e wh en

, ,

a pplic a ble h a nd s a m pling m a y be a ccur a tely p erform ed ; it is

,

still widely used by smelting pl a nts a s it a voids cru shing a l a rge ,

d
2
p a rt of the ore
d
.

Coni ng a n Q ua r ter i ng — The method of co ni ng a n qu a rter

d
.

”
ing h a s been in use for m a ny ye a rs a n is still e m p l o yed but , ,
“
it is being displ a ced l a rgely by the a ltern a te shovel method ”

d d
- .

Coning a n qu a rtering unl ess c a refully p erformed which is iffi , ,

cult to do is a pt to be in a ccur a te In this method t h e thorough

d
.
, ,
.

mi x ing of the ore is essenti a l a n the mi x i ng is su p p o sed t o ,

be e ff ected by coning T h e c o ne is built up by men moving

d
.

a round the circumference Of a circle a n shoveling t h e ore up o n

1
L T W ig h t E l ment f Ch n in th S m pling f O
. . r , e M i n M m III 3 53
o a ce e a o res , . a , ,

3
dd Ma c h in e S a m pl ing A W W k
d I ndt
Fo r a g oo isc ussio n of , co nsu l t . . a r w ic , No tes on

S a mp ling .
"
pub l ish e b y th e u s r ia l P ub Co . .
, D env er , Col o .
38 A M A Nfl A L OF FI RE ASSAYIN G

the poin t o f a cone formed by the a ngle o f rep o se of t h e m a teri a l

fa lling ve r tic a lly u p o n o ne p o in t The s a m pl ers fro m 4 to 8
— .

men move so a s t o be a l w a ys di a metric a lly opp o site ea ch o ther

—

d
.

I n order to fix the p oint of th e c o n e a r o is driven into the ,

gro und as a g uide It is evident th a t the sh o v eling must be

.

very co nscientiously d o ne in order to h a ve the or e distribute

d
itself unifo rmly ( fine a n co a rse) over the su rf a ce of the c o ne ;
but this u niformity is essenti al to th e Obt a ining o f a true s a m ple .

Wh en the cone h a s been built up it is then pull ed d o wn by the

d
,

men w al king a ro u nd the pil e a n scr a ping the ore from t h e a pex
to the b ase until a fla t pl a que of ore is m a de a bout 1 2 o r 1 8 in
,
.

thick Then in the fo rm of a cro ss pl a tes of iro n a r e c a refull y

d
.
, ,

d
centered on t h e p ile a n driven in dividing the pl aq ue into ,

d
qu a rt ers T w o o p p o site qu a rters a r e rem o ved t o the bins a n
.
,

d
the other t w o representing the s a mple a r e r esh ov ele int o a
dd
, ,

d
c o ne a n the oper a tion re pea t ed The ore is th en r ecr u sh e a n .

c o ned a n qu a r tered a g ain until fin a lly a s a mple o f from 25 t o

,

3 0 lb is obt a ined The number of r ecr u sh ing s depends up o n

d
. .

d
the size of the first s a mple a n the n a ture of the o r e The s a mple .

is then ground fine a n p rep a r ed for the a ss a y o ffice by cut ting

down with a split s a mpler o r other a p p ro ved device The wh o le
d d
.

process i s slow a n l a b o ri o us Three m en ca n h a n le fro m 20 t o

.

25 t o ns of s a mple p er shift a t a c o st o f fro m 4 5 t o 50 c ents p er t o n

d
.

T he A lter na te shovel M etho - — The fund a ment al l a w of .

s a mpling m a y b e st a ted th u s : In o rd er t o pro p erl y t a ke a s a m ple

of ore it is necess a ry to t a ke the s a mple frequently or in a s
d
, ,

m a ny p l a ces a s p o ssible a n to t a ke the s a me qu a ntity e a c h

,

ti m e a t regul a r interv al s Th ese c o nditi o ns a r e fulfilled by the

.

”
a ltern a te sh o vel method which is c o nducted a s foll o ws :
d
-
,

The ore from the c a rs is dumped o n a pl a tfo rm a n men with

d
the pro p er siz ed a n sh a p ed sh o vels put it into the bins t a king ,

o u t for the s a mple a cert a in number d ependent o n the n a ture

d
,

size Of the ore p ieces ; e g nine shov els a r e thro wn int o the
d
an . .
,

bins a n every t enth sh o vel is t a ken a s a s a m ple If the o re is .

di fficult t o s a m p le s a mple S hov els m a y b e t a ken m o r e fr equ ently ;

,

o r if the ore is uniform less frequ en tly ,

It is usu a l t o cut o u t .

from one fifth t o one twenti eth o f t h e o r e The a lt ern a te sh o vel

- - -
.

d
m eth o d possesses the foll o wing a dv a nt a ges
. d
1 It is more reli a ble a n a ccur a te th a n c oni ng a n qu a r tering .

2 It is che a per in oper a tion

. .

3 It is q ui cker
. .
 SAM P LIN G 39

The “qu a rtering

the spli t sh o vel meth o d s a re no t d
d
an -

reli a ble a n need no t be d escribed .

A t the pl a nt of the S t a nd a rd S melting Co mp a ny a t R a pid ,

City S Da k the shovel s a mple is p a ssed to a Bl a ke crush er

,
. .
,

with a 9 x 1 5 in mouth opening h a ving a n A di sch a rge so a s to

d
.
, ,

h al ve the crushed s a m ple One of the h a lves is fed i rectly to .

a p a ir of 24 x 1 2 in rolls the disch a rge from which is a g ai n

.
,

a utom a tic a lly h al ved If a 1 00-ton lot is t a ken a s a unit the .

,

s a mple a t this p oint is tons (t a king every tenth sh o vel) with ,

in i n di a meter T he rolls di sch a rge

d
no p a rticle l a rger th a n . .

directly upon a pl a te iro n floor where the o r e is r esh ovele -

, ,

every fifth or tenth shovel being t a ken a s a s a mple which no w ,

d
a mounts t o 1 000 or 500 lb This is p ut thro ugh a p a ir of 12 x
d
.

1 2 in s a mpling rolls a n crushed fine a n then s a mpled by a

.
,

l a rge Jones split o r riffle s a mpler which t a kes h a lves until fin a ll y

d
, ,

d
a s a m p le o f between 1 5 a n 20 lb is a rrived a t This is p ut . .

through a sm al l c o ne grinding mill a n a fter a determin a tion o f ,

moisture o n the s a mple fl oo r is sent to the a ss a y O ffice H ere

d
.

it is cut d o wn to a bout 2 lb by a sm al l J ones s a mpler a n then .

,

crushed o n a buck b o a rd t o p ss a a 12 0 mesh screen fu r nishing

-
,

the a ss a y s a mple This s a mple is supp o sed t o cont ain no mois

.
,

ture a s this w a s elimin a ted on the sa mple floor where the per
, ,

cent a ge o f moisture is determined ; but a s a ll settlements a re

m a de on dry s a mples the fin a l a ss a y s a mple is a g a i n he a ted a t
,

1 00 C for some time in order to expel a ny moisture which the

°
.

s a mple m a y h a ve a bsorbed in its p a ss a ge from the sa mpling

'

works to the a s s a y o ffice The a ss a y s a mple is divi ded into

d
1
.

4 p a r ts a n p ut in p a p er s a cks One p a rt is a ss a yed by the .

s eller Of the ore or product ; one p a r t by the p urch a ser ; a third

p a rt is kep t for em er gency ; a n a fo urth p a rt is l a id a side for a n d
d
umpire a ss a y if such bec o mes necess a ry
, .

The a ss a ys m a de by the seller o f the o r e a n those m a de by

the purch a ser Of the o r e a r e c al l ed contr ol a ssa ys If the
d
.

seller a n purch a ser a gree within a cert a in limit de p ending on ,

the v a lue of th e o r e settl ement is m a de on t h e p urch a se r s a ss ay

,
’
,

o r sometimes on the a v er a ge of the two a ss a ys If they do no t

d
.

a gree it is the pr a ctice fo r the buyer a n seller to re a ss a y their

d
,

o w n s a mples or to e x ch a nge p ulp s a m p les a n rea ss a y If they .

do not then a gree a n umpire a ss a yer is chosen wh o m a kes a n

,

1
G . A . J a mes , E ng . an d
M in . J ca n , X C, 1 04 7 ,
“
Moist ure as a S o ur ce of E rro r in A y ssa
Rep o r ts .
40 A M A N UAL OF FI RE ASSAY I N G

u mp i r e a ssa y,by the results of which a ll p a rt i es a bid e a n on ,

d
which settlem ent is m a de T h e p a rty th a t is f a rthest a w a y .

fro m the result o f the umpire h a s to p a y fo r the a ss a y

d
.

Co ntrols a r e m a de with three check a ss a ys a n umpires with ,

four check a ss a ys In s a m p ling sm a ll l o ts in the l a b o r a t o ry

d
.

d
an cutting d o wn fo r the a ss a y s a m ple t h e principles a l r e a dy ,

d
enum er a ted a lso a p ply R i fl e s a m plers a re comm o nl y use .

a s w ell a s the c o ning a n qu a rt ering method a lthough this l a st ,

is no t recommend ed even f or sm a ll lots T h e fin a l pulp s a mple ,

.

is p ut through a 00 o r 120 me sh screen ; fo r high -gra de m a t er i a l ,

1 -

1 50 to 200-m esh is b etter It is then th o ro ughly mixed o n a .

rubber sheet o r on he a vy gl a z ed p a per spre a d out in a thin , ,

FI G . 37 — J . O N ES R F LE
IF SA MPL R E .

b r o a d pl a que in thick a n sm a ll lots t a ken with a sp a tul a

.
,
d
d
a t r egul a r int erv a ls until the required weight is obt a ined ,
Fig . .

3 7 shows the J ones ri fl e s a m pl er a n Fig 38 t h e U mpire mech a n .

i c a l o r e s a m p ler .

The form with p a ns i s prefera ble to th a t which h a s h a lf of

d
its ri fl es cl o se d 1
The s a m pler s should h a ve a n even number
.

d
o f ri fl es an no t less th a n 1 2 of them fo r best w o rk
,
The .

s a m pling sh o vels should b e o f t h e width o f the s a mpler a n per

fectly str a ight a cro ss the edge so th a t the o r e will f a ll unif o rmly
,
d
int o the ri fl es a n in equ a l qu a ntities int o ea ch ri fl e La rge .

ri fl e s a mplers fo r 4 00 to 500 lb s a mpl es a r e used in s a mpling .

w o rks The ri fl e s a m pler wh en p roperly used is a n a pp a r a tus

.

th a t will do a ccur a te work .

G rea t c a re sh o uld be t a k en t o cl ea n all s a m pling a p p a r a tus a fter

“ ”
s a m pling e a ch lo t so a s t o a v o id s a lting s a mples This a lso
,
.

a p p li es to a ll t h e crushing m a chinery em p l o yed in the s a mpling .

1
L . D . H u nt o o n, A c c u ra c y of M ech a nica l dR
an ifl e Ore S a mp lers , E ng . an d
M in . J o ur .
, X C, 62 .
 CHA PT E R IV

WE IG H I N G ; B A L A N C ES A ND WE IG H TS
—

d
BA LA CE S used i n weighing the minute qu a n
d
N T he . b a l a nce
tities of gold a n sil ver is a delic a te piece of a pp a r a tus a n must
d
be c a refully a dj usted a n h a ndled in ord er t o give a ccura te re
sult s .The b a l a nc e sho uld be set upon a firm found a tion not ,

subj ect t o vibra tio n; otherwise it is a pt t o be frequently thrown

d
out of a dj ustment S tone or concrete p i ers set so me dist a nce
.

“
into the ground a n free fro m the floor a r e the b est fo und a ti o n s ,

when the vibra tions induced by moving m a c hi nery a r e a bsent .

Where su ch vibr a tions occur insula ted sh elf su p ports should

,

be u sed .

Constr u ction The b a l a nce be a m i s m a de Of a luminium gold

—

d
-
,

pl a ted br a ss speci al silver a luminium al loys etc a n a s light a s

, ,
.
,

possible consistent with the requisite strength The m a teri a l

fro m which it is m a de sh o uld be non m d
.

a gnetic a n h a ve a sm al l -
,

c o efl cient of exp a nsion so th a t tempera ture ch a nges will h a ve

,

d
but slight eff ect on the length of the b e a m The p a h a ngers n- .

a r e frequently of a nickel silver a ll oy o r of germ a n silver a n

d
-
, ,

the p a ns Of a luminium The st a nd a rd s a n other met a l work a re

d
-
.

best m a de of gold pl a ted br a ss The knife edge s a n the pl a tes

d
- - .

o n which they rest a r e m a de of a g a te a ccur a tely p olished a n ,

ground t r ue The b a l a nce be a m h a s three knife edges w hi ch

.
- -
,

sho uld be in line in the s a me pl a ne in order t o g ive equ a l sen

sibi it y wit h v a rying lo a ds
l The t w o b a l a nce a rms or the
d
1 -
,
.

ist a nce from the centra l kni fe edge to e a ch of the o uter knife
“
-

edges sho uld be equ a l in len g th This c a n never be a bsolutely

,
.

a ccomplished but ma y be very closely a ppro x im a ted T h e

,
.

a ccom p a nying illustr a tion (F ig 3 9) shows the essenti a l fe a tures

.

o f the b a l a nce .

When the sm a ll weight 177! i s p ut into th e p a n it will c a use a

d
deflection of th e p ointer a n the center of gr a vity Of the b a l a nc e
,

system shifts The conditi o n of equilibrium is th en e x pressed

.

by the equ a tion

M x =m x ’ ’

1 G ottsch a l k , T h e Ba la nce . in West Chem

. . d
M
an a! II Ap il
, r , May a n d
J
une, 1 906 .

42
 B A LA N CE S A ND W E I G HT S 43

39 — . D IA G RA M OF AS S A Y B L N CE
A A .

th e k nife-e g e d
d
centr a l .

knife-e g es
d
. th e o u ter .

m y yste m
d
a j ust ent for cente r o f g r a vi t of th e b a la nce s .

. a j m
ust ent s for equ a l mo ment o f arms .

c ente r o f g r a v ity of th e b a l a nc e syste m .

pointer-arm
d d
.

. istance of fl e ec ti o n o f center o f g r a vi t y , or th e g r a vi t y lever -

ar m
.

lever -a r m o f sm a ll w eig h t m in D3 11
’

sma ll w eig h t.
ma ss of b ala nce system .
44 A MA N UAL OF FI RE ASSAYIN G

F rom thi s it follows th a t if M incre a ses th a t is if the m a ss

d
, ,

of the b a l a nc e system bec o m es gre a ter a n o ther c o nditi o ns ,

rem a in const a nt the w eight m must increa se t o c a use t h e s a me

,
’

d eflection ; i e the sensibility of t h e b a l a nce will be l essened the

. .
, ,

sensibility being the a m o unt of deflecti o n c a used by a given

m a ss A ss a y b a l a nc es must S h o w a sensibility of a t le a st o ne
.

h a lf divisi o n Of the sc a le with a weight of mg or even .

mg This sh o ws the n ec essity fo r a n extremely light co nst r u c

.

ti o n or a sm a ll m a ss o f the b a l a nce system It is evid ent fro m

, .

the equ a tion th a t the sensibility might be preserved by incr ea s

ing x i e by lengtheni ng the a rms Of the b a l a nc e ; in pr a ctic e
’
. .
, ,

however this wo uld al so very m a teri a lly increa se M S O th a t the

, ,

g a in is m o re a p p a rent th a n re a l Lo ng a r m b a l a nces a r e a lso .

very slew of vibr a ti o n Formerly l o ng a r m b a l a nc es were

d
.
,

common but in m o ern a ss a y b a l a nces th e a r m r a rely e x c eeds

,

in .

F rom the equ a ti on it a lso follows th a t if t h e c ent er o f gr a vity ,

o f the b a l a nce system is pl a ced a t A

d
the knife edge x bec o mes ,
-
,

zero a n we h a ve
M XO= m x ; Or m x

or m ap pro a ch es 0 for x is p r a ctic a lly c o nst a nt ; in Other w o rds

’
,
’
,

t h e b a l a nce will bec o me ex trem ely s ensi t ive a n infinit ely sm a ll ,

w eight in the p a n c a using rot a ti o n While the b al a nce w o uld

d
.

be ve r y sensitive it wo ul d a lso be ve r y unst a ble a n ,

cr a nky .

In designing b al a nces it is hence very im p ort a nt t o preserve a

me a n between high sensibility a n st a bility a n a s this l a tter is d ,
d
o bt a ined m a inly by lowe ring t h e center o f gr a vity which l essens ,

d
sensibility in p a rt by increa sing frictio n o n the knife edges
, ,

these must be constru cted with e x treme c a re a n must b e a s ,

n ea rly true a s possible Most a ss a y b a l a nces a r e provid ed wi t h

.

f a ll a w a y p a n rests oper a ted by a th umb sc r ew o n the out side

o f the c a se When this screw is turned t o t h e l eft the rests dro p
d
.
,

a w a y f r o m the p a n a n o n fu r th er tu r ning the b a l a nce b ea m is

dd
,

l o were a n set free so th a t the centr a l knife edge rests on its

,
d
be a ring a n the b a l a nce is fr ee t o a ct .

The screw b all D is pro vided t o a dj ust the c enter of gr a vity

-
,

which sho ul d be so mewh a t below the knife edge A T h e c ent er - .

of gr a vity is a dj usted so th a t a w eight of mg in t h e p a n o r .

o n the be a m will c a use a deflecti o n o f from o ne h a lf t o o ne divi

-
 B ALA N CES A ND W E I G HT S 45

si o n Of the p o int er The l o wer the c enter o f gr a vity of the b a l a nce

.

system the m o re r a pid th e oscill a ti o n o f t h e b a l a nc e T h e

,
.

higher o r t h e n ea rer the p o int o f suspensi o n th e sl o wer the o scil

d
,

l a t io ns a n the grea t er the sensibility .

Weig hi ng Before weighing the b a l a nce is a lw a ys th o ro ughly

— .
,

cle a ned in ev ery p a rt fro m dust by a s o ft c a mel s h a ir brush ’

d
-
,

m a de p erfectly level by a dj usting the l eveling screws a n the ,

”
p o inter st a nd a r dized t o O by t h e little thumb screws C C
d
-
, .

T o o this the b a l a nce is set in m o ti o n until the p o inter swings

,

t o from 5 t o 8 divisi o ns o n the sc a le e a ch side of the z ero

m a rk . If the b a l a nce a r ms a r e equ a l in moment the p o inter
-
,

will swing p r a ctic a lly a n equ a l number Of divisi o ns on e a ch sid e ,

l o sing h o wever a trifl e o n e a ch swing thus : + 8

d
, , , ,

etc t h e loss being due to frictio n a n to a

.
,

gra d ua l settling b a ck into eq uilibrium If the swings a r e no t a s .

o utlin ed the a dj ustm ent is m a de until th ey b ec o me so The

d
.
,

b a l a nc e is th en tested fo r sensibility a s d escribed a n the a dj ust ,

m ent m a de fo r it if ne c ess a ry by m ov m g the c enter of gr a vity

, , .

If th e b a l a nce a rms a r e suspected of being unequ a l in length

-

th ugh this is r re in g d b l nc s weighing by “ i

( o a oo a a e ) su b st ,

t u t io n o r d o uble w eighing is a d o pt ed In this method the

d d
-
.
, ,

Obj ect t o be w eighed is pl a ced fi r st in o ne p a n a n weighed a n ,

th en in the o th er the t ru e wei g ht b eing t h e squ a re ro ot Of the

,

p r o duct Of the t w o weights found Wh en the sensibility o f the .

b a l a nc e is a ccur a tely kno wn no a dj ustm ent for equ a l m o ment

,

Of a rms n eed be m a d e b ut weighing m a y be d o ne by d efl ec ti o n

, ,

a fter t h e tru e zero o r equilibrium p o int is fo und This is fo und

d
.

a s f o ll o ws : S t a r t t h e b a l a n c e swinging a n c o unt s w ings t o th e

d
l eft a s m inus a n t o t h e right a s plus S upp o se t h e swings a r e .

a s f o llows : — 8 +3 ,
T h e zero p oint th en is
,
-

(divisi o ns) .

( divisi o ns ) .

or the true zero o r true point o f rest is

,
divisio ns t o t h e
l eft o f t h e z ero m a rk o n th e sc a l e .

Th en pl a c e t h e p a r ticle t o be weigh ed o n the r ight h a nd p a n

d d
-

weigh a g a in t o et erm in e th e p o int o f r est und er these co n

d
an

itio ns The swings a r e a s foll o ws :

. 10 + 2 The sensi , ,
 '

46 A M A N UAL OF FI R E ASSAYIN G

bility o fthe b a l a nce being divi sion deflectio n fo r e a ch mg .

t h e new zero p oin t is

-

(divi si o ns)
2

( divisions) ,
new po i nt Of re st ,

dthe weight of the p a r ticle is the di fference in deflecti on

d
an

between the t w o p o ints of rest (3 8 7 5 2 3 7 5 — ivision)

,

d
divided by or mg In pr a ctice in pl a ce o f two re a dings
.
,

one on the other of th e zero i t is b etter to m a ke

d
o n one side a n ,

three a n t w o re a di ngs respectively .

Thi s method however is not gener a lly to be r ecommended ;

, ,
“ ”
the rider should be u sed fo r the d etermin a tio n of the fra ction a l
p a rts of the milligr a m The b a l a nce sh o uld a lso be a dj usted for
d
.

equ a l moment of a rms a s escribed befo re weighing

, ,
.

In order t o detect inequ a lity in the len g th Of the a rms st a nd

d
,

a r iz e th e b a l a nce t o the tru e zero pl a ce a 1 gr a m weight on the

d
-
,

right p a n a n a n old or worn 1 gr a m weight o n the left pa n

d
-
, ,

an bring the b al a nce into a ppro x im a te equilibrium by a dding

minute qu a ntities Of old rider Wire to the short weight .

Let the gr a m weight in the right p a n be c a ll ed A .

d
Let the counterp o ise in the l eft p a n be c a ll ed B .

Let R be the right lev er a r m a n L the left lever a rm

- - .

D etermine the zero p o int of the b a l a nce in the m a nner de

-

scribed If this zero p oint di ffers fro m th a t o f the unl o a d ed

d
.
-

b a l a nc e bring the b a l a nce t o the Ol z ero p oint by moving the

,
-

rider on the left or right a r m a s required ,

.

Let the w eight indic a ted by the rider be c a ll ed + m or — m ,

a s it m a y a ct with or a g a inst B t o bring the b a l a nce system

b a ck to the o r igin a l zer o p o int

d
-
.

Now shift the weight A to the left p a n a n B t o t h e right

p a n ; remove the rider a n a g a in d ed
termine the z ero p oint a n -
,
d
then m a nip ul a te the rid er t o b ring the b a l a nc e syst em t o the
zero p oint Of t h e u nl o a d ed b al a nce a n c a ll t h e weight indic a t ed
-
d
by the rider i n a s it m a y a ct with or a g a inst A
,
The fo ll o wing .

equ a ti o ns will th en result :

BR = (A i n) L
 B ALA N CES A ND W E I G H T S 47

L A +B
3 . A +B
R
L i mi n L i mi n
’
or ,
a pp roxi m a te1y
R A B i mi n R 2A

If m — n
,
or the revers a l of the m a sses shifts the zero
p o int ex a ctly as much t o one side a s it w as befo re on the o ther
L L
of the a ctu a l o, the b al a nce has e qu a l a rms ; i . e .
, 1 . should
R '

R
not exceed 1 1 0 000003 .

S ome a ss a yers weigh by no deflection They a dj ust the .

b a l a nce to the true zero pl a ce the be a d t o be weigh ed in the

d d
,

right h a nd p a n a n then by the a dditi o n of wei ght s a n t h e

d
-

m o ving of the rI er by re p e a ted tri a ls b al a nce the b ea d so th a t , ,

fina lly when the b al a nce is l o wered gently o its kni fe edge no
,
n -
,

d
deflection o f the p ointer t a kes pl a ce This method however is
d
.
, ,

no t rec o mm ended as it disreg a rds friction a n i nerti a, a n for

,

sm a ll weights gives in a ccur a te res ults .

PR A CTI C AL NOT E S ON T HE A SS A Y BA LANC E In those l a bor .

a t o r ies where the b al a nce c a nn o t be supported o n stone p iers

trouble ma y be ex p erienced from j a rring o f the b a l a nce Thi s .

ca n l a rgely be elimin a ted by su p p o rting the levelling screws on

d
trunc a ted p yr a mids cut ou t of rubber p a c king m a king the l o wer ,

b a se of the suppo r t 2 in squ a re a n the u p per one 1 in squ a re

. .
,

with a thickness of a bout 1 in A sm a ll squ a re of ground gl a ss .

m a y be ce mented to the to p of e a ch su pp o r t to t a ke the thrust Of

the levelling screw A nother method of a voiding the j a r is to
d
.

bore fo ur h oles } in deep into the b al a nce t a ble t o p a n inse rt

.
,

N O 5 r ubber stoppers on to p of which a sm a ll p iece of he a vy

.

sheet le a d is pl a ced a bout 2 in thick The level screws sho uld

,
. .

3
be sunk into the le a d a bout 1 , in deep for the best eflect
'
l
. .
,

One source Of troubl e with delic a te a ss a y b a l a nces is th eir

tendency to become m a gnetized or ch a rged with st a tic electricity
which will c a use them t o a ct in a very err a tic m a nner du ring
w eighing Ba l a nce be a ms c o nstructed of m a t eri a l subj ect t o
.

m a gnetiz a ti o n should be a v o id ed When a b al a nce of this .

kind is in use it ma y become necess a ry to ch a nge its p osition t o

a v o id in p a rt the m a gnetizing f o rces Fo r inst a nce the b a l a nce
d
.

be a m should no t be p a ra llel t o a n o rth a n so uth line Ba l a nces .

c o nstru cted o f no n m a g netic m a teri a l ma y be subj ec t t o simil a r

-

D M Lid
1 d .ll E ng
. ndM i n J n LXXX I X 305
e , . a . oa , , .
 A M A N UAL OF FI RE ASSAY I N G

tro uble due t o ch a r ges o f st a tic electr i ci t y This is p a rticul a rly

d
.

tru e in hot dry clim a t es a n m a y b e a ccentu a ted by insul a ting

,

the b al a nc e fro m its su r ro undings by gl a ss o r rubber sup p o r ts

d
.

When troubl e o f this kind occu r s it m a y be esir a ble t o ground

the b a l a nce by a c o p p er wi r e Ba l a nces which h a ve p a ns th a t
d
1
.

a r e bl a ckened o n o ne side a n a r e bright o n t h e other seem to be ,

subj ect to p eculi a r disturb a nce a t c ert a in times In this c a se .

b o th sides of th e p a n sh o uld b e bl a ckened .

Fm . 40 — . PU LP B A L A N CE .

It is nec ess a r y t o h a ve a n ev en t emper a ture in t he b a l a nce

r oo m p refe r a bly a b o ut 6 0 F S unl ight sh o ul d be ex clud ed if
°
.

p ossible The. b a l a nce must no t be ex pos ed t o a so u r ce o f h ea t

which will r a di a te unsymm etric a lly o th er wise unequ a l ex p a nsi o n ,

o f b a l a nc e a rms will c a use in c o rrect w eights

- In weighing t h e .
,

b a l a nce d oo r sh o uld a lw a ys be cl o sed t o a v oid the disturbing

-

eff ect o f slight a ir currents The t r u e w eight of a m a ss c a n b e

d
.

et ermined o nl y by c o rr ec ting f o r t h e bu o y a nt eff ect o f air T he .

er r o r h o wev er is so sm a ll th a t it m a y o r din a r il y b e n egl ec t ed

2

d
.
, ,

Pulp a n re a gen t b a l a n c es a r e sh o wn in Fig 4 0 T h e o r din a r y . .

type of a ssa y butt o n b a l a nc e is illust r a t ed in Fig 4 1 Fig 4 2 . . .

1 A A tin nd S w i f t H nt B l n M nd S i P XCVII 2 24 c r ess ,

and
us a u er , a a ces , a

O tw ld Ph y i Ch mi l M
. .
.
.
,

2
s a , s c o- m nt
e 1 89 4 p 3 8
ca Am ea sur eB li A e s,
”
, . . es ss.

M nu l f E x p im nt in Ph y i
a a o er e sp 151 s cs , . .
50 A MA N UAL or F I R E A S SAYIN G

d
they ar e not so rea dily inj ured by h a ndling R iders a re fre .

quently sold which are not of tr ue weight a n it is essenti a l t o ,

The s a me is tru e of weights It is

d
c heck them before using . .

esira ble for every assa y o ffice to h a ve a set of st a nd a rdized

FI G . 42 —.N0 N -Co L U M N TY P E or A SSA Y B A LA N CE .

( K e llen )

FI G . 43.
— PL A TI N U M A
SSA Y W EI GHTS .

weights for comp a ris o n These st a nd a r dized weights c a n b e

.

p urch a sed fro m th e b a l a nce firms ; or a set ma y be c o rrect ed by

the G overnment Bure a u o f S t a nd a rds 1
.

1C n lt Ci
o su l N 3 U S B
r cu a r f S t nd
o. , dD pt f C mm ndL b
. . ur ea u o a ar s, e . o o er ce a a or ,

Washing to n . D C. .
 B ALA N CES A ND W E I G H TS 51

stem — dss y ton

d
T he A ssa y ton S y - G ra m
weights a re an a a -

used to weigh p ul p a n fluxes The a ss a y ton system w a s de

- .

vised by Pro fess o r Ch a rles F Ch a ndl er of Columbi a U niversity

d
.
, ,

New Yo rk a n reconciles the di fficulties a rising from the f a ct

,

th a t a ll ores etc a r e weighed by the a voirdupois system While

,
.
, ,

preci o us m et a ls a r e weighed by the troy syste m The b a si s of .

FI G . 44 — . A SS A Y T ON W E I G HT S .

FI G . 45.
— G RAM W EI G HT S .

the a ss a y ton is the number of troy ou nc es in 1

a voirdup o is .

1 ton 2000 lbs ; .

1 lb (a voirdup ois) = 7 000 troy gr a ins ;

.

theref o re 1 t o n
,
troy gr a ins .

1 o z (tro y) . 4 8 0 gr a ins ;
52 A M A N UAL or F I RE ASSAYIN G

Then t a king 1 mg a s th e unit 1 a ss a y ton mg

d
.
, , .
,

or gr a m s a n 1 mg be a rs the s a me rel a tion t o 1 a ss a y

,
.

ton a s 1 o z tro y be a r s to 1 ton of 2000 lb a voirdupoi s

d
. . .

F ro m this it f oll ows th a t if 1 a ss a y ton o f ore is t a ken a n

d
,

the sil v er a n g old from this IS weigh ed I n milligr a ms this weight ,

W ill represent ounces troy p er t o n of o r e Fig 43 sh o ws a set of

d
. .

pl a tinum a ss a y weights Figs 44 a n 4 5 S how a set of a ss a y ton

d
.
-
,

an gra m weights res pectively

,
.
 CHA PT ER V

R E DUC T I ON A N D OX I D A T I ON R E AC T I ON S

RE D U T O
C I N — A reduction re a ction a s p a rticul a rly defined
.
,

fo r a ss a ying is one in which a met al is reduced from its com

,

p o unds by s o m ereducing a gent The ch emic a l definition is a lso .

a pplic a ble in th a t in a ss a ying we frequently reduce a com p ound

, ,

fro m a st a te of higher oxid a tion t o a lower st a te of oxid a ti o n by .

me a ns of a reducing a gent .

A n oxi d a tion re a cti o n is one in which a met a l or a com

pound is ch a nged t o a comp ound of a high er st a te of oxi d a tion ;
for ex a m p le Pb to Pb O S to S O, or Ph O to Pb O, R educti o n
d d
.
, , ,

an o xid a tion re a cti o ns frequently occur in a ss a ying a n it is ,

d
essenti a l th a t the a ss a yer be th o ro ughly f a mili a r with the theo ry

an d f a cts In spe a king of reducing a gents a n reduction with

.

sp eci a l reference to a ss a ying w e h a ve chiefly in mind such r e ,

a gents a s reduce met a llic le a d from lith a r ge in the crucible The .

chief of these a r e : ( 1) a rgo l (2) ch a rc o a l or coke o r c o a l dust (3 )

, ,

fl o ur o r sug a r Thes e a r e a dded t o the ch a rge in su fli cient qu a n

.

tity to pro duce th e p ro p er siz e of le a d butt on in the cru cibl e

d
a ss a y It often h a p p ens th a t a n o r e will c o nt a in reducing a gents
d
,
.

chiefly sulphides so th a t it bec o mes unnecess a ry t o a

,
a n ex

t r a neo u s a gent In f a ct it m a y c o nt a in a n excess o f reducing

.
,

a gent requiring a n o x idizing a gent t o destr o y the excess

,
.

The reduction of l ea d by a rgo l is exp ressed by the follo w m g

equ a ti o n

1 0 Pb O 2 KHC, H, O, 1 0Pb 5E , O K, O 80 0 2
3 76 2070
One g r a m of rgol will reduce
a gr a ms o f le a d fro m or

m ore gr a ms of Pb O The a b o ve formul a fo r a rgol is th a t of p u r e

.

bit a rtr a te of p ot a ssium A r gol c o nt a ins a s impurity a c ert a in

.

a m o unt of c a rbon a c eo us m a tt er so th a t its reducing p ow er will ,

d
be incre a sed It Will be found th a t the a ctu al reducing p o w er
.

o f 1 gr a m of a rgol v a ries between 7 a n gra ms o f le a d d ep end ,

ent o n the a rgo l used .

T h e reduction o f l ea d by ch a rco a l is ex p ressed by the f o ll o wing

re a cti o ns :
2Pb 0 C 2Pb co ,
12 4 14
53
54 A M A N UAL or FI RE ASSAYIN G

On
e gr a m of c a rb o n will reduce gr a ms of Pb A S ch a r .

co a l co a l or c o k e dust will co nt a in m o re or less inert a sh which

,

h a s no reducing e ffect the a ctu al a mount o f le a d reduced will be ,

d
m a te ri ally less It will usu a lly be found to r a nge between 20
.

a n 3 0 gr a ms p er gr a m of c a rbon a c eous reducing a g en t used .

Flour will reduce from 9 to 1 2 gra ms of l ea d per gr a m de ,

d
p ending on the n a tu r e o f the flour .

The common sul phides most frequently found in ores a n ,

which give the ores c o nt a ining them reducing p o wers a r e : Pyrite ,

p yrrhotite (Fe7 ss) a rseno p yrite (FeA sS ) ch a lco p yrite

d
, ,

ch a lcocite stibnite (s ss) g al en a (Pbs) a n , ,

sph a lerite (Z nS ) .

d
The a mount of le a d reduced p er gra m of the respective sul
p hi es v a ries a ccording to the combin a tion of conditions which ,

will be fully discussed .

d
T a king pyrite a s a n ex a mple the foll o wing equ a tion e x presses ,

the re a ction which t a kes pl a ce when it is fused with sod a a n

lith a rg e :
( )
a 2FeS 2
1 5P b O = Fe, O,
4 8 0 ,
1 5Pb
24 0 3 10 5
( )
b 4 8 0 3 4 Na zCO8 4 Na , S O4 40 0 2
One gr a m of pure pyr ite r edu c es gr a ms o f le a d The .

result ca n re a dily be o bt a ined by the f ollowing ch a rge :

3 gr a m s
Na CO , , 1 0 gr a m s
Ph O . 1 00 gr a m s

The result could not be o bt a ined wer e t h e pyrite t o be fused

with lith a rge a lone a s the presence o f s o d a a stro ngly a lk a line, ,

b a se induces the form a ti o n of sulphuric anhydride (S OS) which

, ,

d d
combines with so d a t o form s o dium sulph a te (N This
sodium sulph a te will fl o a t on t o p o f the sl a g a n is not eco m
posed by the temper a ture usu a lly a tt a ined in the mu ffle It .

sep a r a tes out on cooling a s a fused white m a ss Its melting .

point is 88 5 C 1
Wh en t h e o x idizing a cti o n in the a b o ve ch a rge
°
.

is diminished by decre a sing t h e lith a r ge t o below 70 gr a ms

d
2
,

the iron is o nl y p a rti a lly o x idized t o the ferric condition a n the

two following equ a ti o ns express the rea cti o ns : 3

W P Whi t A m J S i XX VIII 4 7 1
T h R dti n f L d
1 e,
. . . ou r . c " , .

3
E H Mi l l f m Li th g in T n A I M E XXXI V
"
. . er , e e uc o o ea ro er a e, ra s . . . . .
, .

d d xi d
3 95 .

I t must be b or ne in mi n k iz ing
dd
th a t w hile w e sp ea of a re uci ng or an o

y ”
th e ir o n
xid
iz d
r ea c t io n th e r ea c ti o n is r ea ll
, of b o th na t ur es , fo r w h ile li th a r g e is re uc e ,

pyrite is "
o e .
"
 RE D UC T I O N A ND o x I DA T I ON REAC TI O N S 55

FeS , 7Ph O FeO 2S O8 7Pb

2FeS , 1 5Pb O= Fe3 0 3 4S Oa I 5Pb
The first equ a ti o n will give 12 gr a ms of Pb p er gr a m of pyrite
d
,

an the second will give gr a ms The a cc o mp a nying t a ble .

gives the reducing powers of the v a rious subst a nces a s deter

mined by the lith a rge sod a ch a rge given for pyrite -
.

TA B LE II .
— RE D UC I N G POWE R S OF AG E NTS

Na m e of r educ ing a gent

du cing a gent
re

Ta b le

Pyrr hot it e . . 1’

S t ib nit e .

Cha lcoc it e . . CV l
S p ha ler it e . .
5 .

Wh en no sod a is present to induce th e fo rm a ti o n of al k al ine

sulph a tes the foll o wing re a ction t a kes p l a ce sulphur dioxide
, ,

S O
( 2) being f o rmed :

R es, + 5Pb 0 = FeO + 2so , + 5Pb ;

1 20 1 03 5

or gr a m of pyrite reduces
1 gra ms o f l ea d .

In the a ss a y a s o rdin a rily p erfo rmed the fo regoing conditions

d
, ,

a r e mo ified by the presence of other subst a nc es, in the m a in

d
d
by silic a Le a d oxide re a dily forms silic a tes with silic a a n the
.
,

mo no b i a n tri silic a tes a r e e a sily fusibl e while those of a

-
,

higher degree a r e fusible with di fficulty When a reducing a gent .

( rgol sulphides etc ) is fus d with silic te f le d with

d
a , e a ,
a o a .o r a ,

ch a rge cont a ining lith a rge a n silic a only a little le a d i s reduced ,

d
when the silic a is present in a mounts to form a trisilic a te o r a bove ,

an o nl y somewh a t m o re when the silic a is present in a mounts

to form a m o no or bisilic a te The re a so n for this is th a t the .

silic a tes of le a d a r e no t reduced by sulphides or c a rbon a ceou s

reducing a gents a t temper a tures below a bout 1000 C ° 1
A bov e .

3 Co nsul t M eta ll ur g ic , I v. 647 .

56 A M A N UAL O F FI RE ASSAYIN G

th a t tem p er a ture reduction t a kes pl a ce more re a d ily T h e .

higher the silic a te degree t h e m o re di ffic ult is the reducti o n If .

,

however cert a in other b a ses such a s ferrous oxide (FeO) sod a

, , ,

or lime (Ca O) a re present (as is t h e c a se with m o st

,

ores) reducti o n o f le a d fro m the silic a te occurs with f err o us

, ,

oxide or s o d a a t a c o m p a r a tively lo w tem p er a ture ; but with

,

lime al one only a t a high tem per a ture The foll o wing equ a tion
,
.

express es this c o nditi o n :

Pb , S iO, 2FeO C Fe, S io, 00 , 2Pb

N o di fficulty is enc o untered in r educing l ea d from the bor a te s
of d
le a d a n so d a by the ordin a ry reducing a gents a t 1 1 00 C
, ,
°
.

While so d a influenc es the a mount of le a d reduc ed fro m lith a rge

by the sulphid es p resent it h as not th a t influ enc e on c a rb o na ce
,

o u s reducing a gents except in so f a r a s it m a y r educe the a cidity

d
,

o f the ch a rge a n thus f a v o r reduction .

The following ch a rge g a ve results a s t a b ul a ted bel o w : 1

R ed uc ing a gent 1 gr a m S o di u m ca r b o na te .

Lit ha r ge 45 gr a m s S i lic a .

Pyrite in this t a ble shows a redu c ti o n of

, ,
gr a ms of le a d
p er gr a m a figure t o b e e x p ec ted when its sul p hur go es o ff p a rtly
d
,

a s S O2 a n p a rtly a s S O3 If the so d a in t h e prec eding ch a rge

.

is increa sed t h e l ea d button will a ppro a c h t h e m a x i m um r e

d
,

u cib le by py r ite .

TA B L E III .
— RE D UC I N G POWE R OF AG E NT S

Q ua nt it y of lea d duced
re

Na m e o f r edu cing a gent by 1 gr a m o f r ed u c i ng

a gent

NO T E — Co m pa r e Ta ble II w it h t his
. .

“
d d
T h e R e u c tio n o f Lea fr o m Li th a r g e T r a ns A I M E XXX I V 3 9 5
dd d
.
, . . . .
, .

D ue to th e r ea y istilla tio n o f sulph u r th is fi g u r e is iffic ul t to o b t a in ; 1 g ra m

d
of

d
,

sul ph ur w ill usu a lly re uce 6 or 8 g r a ms o f lea .

58 A MA N UAL OF FI RE ASSAY IN G

the g a s c a ught from th e fusi o n sho wed p e r c ent o x ygen the .

,

b a l a nce being nitrogen Oxides of nitrogen were a bs ent This

. .

indic a tes th a t when niter is used in the crucible fusion o x ygen ,

is evolved which under ce r t a in c o nditi o ns ma y esc a pe fro m the

, ,

cha rge without re a ction A s al re a dy st a ted the ni ter will re a c t

.
,

with the reducing a gent ; e x pressing it s o x idizing power in term s

o f le a d is merely fo r convenience In cert a in types of ch a rges
d
.
,

those cont a ining lith a rge ni ter a n reducing a gent o r

d
i a
. .
, , , ,

lith a rge sod a ni ter a n reducing a gent pr a ctic a lly theo retic a l
, , , ,

results m a y b e obt a ined ; e g the o xidizing power o f niter a s . .

,

c o mp a red to ch a rco a l is exp ressed by the foll o wing equ a tion

or 1 g ra m of
niter oxidizes g r a m o f c a rbo n .

T a king the r educing p ower of p ure c a rbon a s gr a ms o f

le a d the o xidizing power o f niter a g a inst c a rbon expressed in
, ,

terms of le a d is o 1 5 x 3 4 5 or ,
gra ms Ten fusi o ns of a
. .
, .

ch a rge compo sed of 8 5 gra ms Pb O 1 gr a m ch a rco al 3 gr a ms , ,

KNO3 with 5 g r a ms Pb O a s a cover ga ve very concord a nt

d
, ,

results a n showed the o xidizing power of niter t o be

,

The reducing power of the ch a rco a l w a s determined by five

fusions with the s a me ch a rge o mitting the KN Th ese ,

results of c o urs e ca n a ls o be o bt a ined by a n impure ch a rc o a l ,

, ,

fo r t a king one which h a s a reducing p o wer o f 26 gr a ms of le a d

,

(this w as used in the a bove fusi o ns) it then c o nt a ins ,

gr a m pure c a rb o n If 3 gr a ms of niter h a ve been a dded.

t o the ch a rge the a v a il a bl e c a rbon for reduction will be

,

( 3 X 0 1 5) or . gr a m whi c h will r e duce X 0 3 1 5 or ,

.
,

5 gr a ms of le a d
,
The oxidizing p o wer o f niter e x p ressed in
.

l oa d then is
, ,

26
or gra ms .

3
Consid ering sulphide a n niter a n it is in this c o nnecti o n
a d ,
d
th a t niter is a lmost inv a ri a bly used the fo ll o wing re a c ti o n t a k es ,

pl a ce in the lith a rge sod a ch a rge al rea dy m enti o ned

-

N a , so , + 0 0 2
or gr a m of ni ter o x idizes
1 gr a m of pyrite In t h e lith a rge .

sod a ch a rge 1 gr a m o f pyrite r educes gr a ms of l e a d ; there~

T hi find
,

ing confi m th a t of E H Mill

s r in T m A I M E XXXI V 3 95
s . . er , ra . . . .
. .
 RE D UC TI O N A ND O XI DA TI O N REACT I O N S 9

fore 1 gra m o f niter in this inst a nce wo uld o x idize 1 2 22 x 0 3 9

,
. .
,

1
or gra ms of l ea d The a cc o mp a nying t a bl e S h o ws a ctu a l .

results o bt a ined fo r the oxidizing power o f niter a g a inst di ff erent

reducing a gents .

TA B LE I V .
— OXIDI Z I NG POWE R OF NI TE R

Ox idi zing p ow er of n iter

R ed u c i ng a gent in term s of lea d

O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O

O O O O O O O O O O O O O O O O O O O O O O O O O O O

O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O

It follows the refo re th a t the oxidizing power of niter v a ries

, ,

with the re duc ing a gent used

d
.

When the a ss a y ch a rge cont a ins silic a a n bor a x gl a ss t h e ,

a bov e fi g ures no longer h old for in their presence oxygen is ,

evolved by the niter which esc a pes fro m the ch a rge as in t h e , ,

c a se of the oxid a ti o n of met a llic l ea d by niter The a mount o f .

o xygen lost (thus reducing the oxidizing pow er of ni ter) is pro b

a bly a function of the r a te of rise o f temp er a ture but evidence ,

a lso points to the f a c t th a t silic a re a cts with the nit er setting ,

free o x ygen a t a tempera ture very close to th a t a t which niter

,

re a cts with ch a rc o a l o r at which o x ygen will re a ct with c a rb o n ,

.

Niter fuses a t 3 3 9 C but does not give o ff o x ygen when fused °

.
,

a l o ne until 53 0 C is re a ched Ch a rc o a l ignites a t temp er a tures

° 2
. .

r a ng ing fro m 3 4 0 C to 700 C depending upon the temp er a ture °

.
°
.
,

a t which it w a s burnt whil e silic a b egins to re a ct wit h niter a t ,

very ne a rly 4 50 C prob a bly a ccording to the following re a cti o n :

°
.
,

Thus duri ng the period in which the tempera ture in the

,

crucible gra du a ll y rises t o a yellow hea t (th a t o f the mu ffl e) ,

o x ygen esc a pes during the r a nge from 4 00 C t o 500 C et c ° °

. .
,
.
,

this l a st being t a ken a s a n a ver a ge tempera ture a t which

ch a rco a l will begin a ctiv ely t o o xidize 3
.

3
Fr o m a nu mb er o f e xp er i ments b y th e a u th or , w illow ch a rco a l w as f
oun d t o beg in
y
d
r eac ti o n w i th ni ter a t v er c lo se to 440
°
C .

T his is o fiere
'

te nta tivel y , as a n e xpl a na tion of wha t occurs.

60 A M A N UAL OF F I RE ASSAY IN G

Ni t er will begin to re a ct with a rgol dpyrite

an at pr a ctic a ll y
its melting point - .

The oxi dizing p ower of ni ter a g a i nst ch a rc o a l in ch a rges

cont a i ning silic a will frequently v a ry between an gr a m s d
o f le a d a v er a ging a bout 4 gr a ms
,
This is gr a ms lower th a n
.

in the lith a rge sod a ch a rge -

The oxidizing p o wer of ni ter
.

a g a inst sulphides is but little l o wered by the presence of silic a or

d
bor a x gl a s s When the oxidizing power of niter a g a inst pyrit e
.

( sulphides) is considered a n expressed in terms o f le a d t h e

d
, ,

v a rying reducing p o wer of su phi es in di ff erent ch a rges h a s t o be

t a ken into a cc o unt T a king a s a n ex a mple a ch a rge cont a ining
.

c o nsider a bl e silic a so th a t a l a rge p a rt of t h e sod a ( a lk a line b a se)

,

is a bsorbed a s a silic a te le a ving but little to f o rm sulph a te

,

from the o xid a tion o f t h e pyrite it is fo und th a t the reducing

,

p o wer of pyrite is 9 gr a ms of l ea d a s a l r e a dy noted In this ,

.

ch a rge niter will re a ct with pyrite as follows :

,

4FeS , + 1 0KNOs 4FeO 5 K3 S O, 38 0 2 5 N3 ;

or 1 g ra m of niter o xidiz es gr a m pyrite T h e o x idizing .

power of niter expressed in le a d is then 9 X 0 4 75 o r gr a ms .

,
.

A ctu a lly it will be ve r y littl e l o w er th a n this a s but little o x ygen

, ,

esc a pes with o ut a cti o n The a ctu a l figure o bt a ined by ex per i

.

ment is very cl o se to
It is evid ent fro m this th a t t h e o x idizing p o w er of niter v a ri es
with the type of ch a r ge used It r a nges fo r pyrit e fro m a b o ut
.
, ,

4 gr a ms in a cid ch a rges to in b a sic ch a r ges (c o nt a ining no

silic a ). It v a ries still more with oth er sulp h id es It h a s b een .

the p r a ctice of a ss a yers in m a king the niter fusi o n to run a p r e

li m in a ry a ss a y in a comp a r a tively b a sic ch a rge (a ppro x im a tely
d
the lith a rge s o d a typ e) a n use the fi g ure o bt a ined fo r the r e
d
-
,

ucing p o wer o f the o re in this ch a rge in c a l c ul a ting the a m o unt

o f nite r for the fin a l fusi o n usu a lly m a d e quite a cid

,
In thi s .

w a y discord a nt results a r e o bt a ined fo r b o th the reducing p o wer

d
,

o f the ore a n the oxidizing p o wer of niter v a ry in the di ff erent

c h a rges .

S u p p o sing th a t the p relimin a ry a ss a y showed the redu c ing

power of a ne a rly pure pyrite t o be 1 2 gra ms o f l ea d per gr a m
o f ore . U sin g a a ss a y t o n in the fin a l f usi o n o n this b a sis ,

the a mo unt o f le a d reduced woul d be 1 2 x l 5 o r 1 8 0 gr a ms ,

.

S ubtr a cting t h e weight o f the l ea d butt o n 20 f r o m this le a ves , ,

t h e equiv a lent o f 16 0 gr a ms of le a d t o be o xidized T a king a .

 RE D UC TI O N A ND O XI DA TI O N REAC TI O N S 61

as the o x idizing p o wer of niter in the fin a l ch a rge 4 0 gra m s of ,

niter would be a dded But in the fin a l ch a r ge owing t o its .

,

a cidity the reduci ng p o wer of the pyrite is but 1 0 gr a ms o f le a d

d
,

p e r 1 gr a m of ore a n the t o t,
a l reducing p o w e r of a ss a y ton
is 1 50 gr a ms It th erefo r e follows th a t the fin a l res ul t will show
.

no butt o n The o xidizing power fo r niter which shoul d h a ve been

d
.

used is 9 x 4 or
1 2
,
an 3 1 gr a ms o f niter a dded This then .
, ,

would give a p p ro xim a tely the pro per sized button A s the .

r a nge of reducing power fo r p yrite is fro m a b o ut 9 to r ms

d
g a

o f le a d a cc o r ding t o whether the ch a rge is a cid a n cont a ins

'

little so d a or is of the lith a rge so d a type the m o st s a tisf a ctory

d
d
-
, ,

w a y to det ermine the a mount of niter t o a is to h a ve the n a ture

of the prelimin a ry ch a rg e t he s a me a s th a t of the fin a l ch a rge
d
,

a s the o x idizing p ower of niter

1
an then use the figure 4 t o .

The foll o w ing ch a r ges a r e recomm ended to determine oxidizing

an d
redu cing powers
PR E LI M I N A R Y A SS A Y N o 1 ,PR E LI MI N A R Y ASSA Y No 2
.
, .

5 gr a m s of p yr i t o us or e 5 gr a m s o f p yr it ous o re
8 gr a m s o f S iO 2
8 g r a m s o f S iO ,

1 00 gr a m s o f Pb O 1 00 g r a ms of Pb O
12 gr a m s of Na CO z , 1 2 g r a ms of Na CO , ,

Borax gla ss co ver 3 g r a m s o f K NO ,

B ora x gla ss co ver

The di ff erenc e in weight o f t h e le a d butto ns o f p relimin a ry
a ss a ys N os 1 a n . d
2 divid ed by 3 will giv e the oxidizing p o wer
, ,

o f ni ter in the type o f ch a r g e used T h e w eight of t h e butto n o f

.

prelimin a r y a ss a y N o 1 divided by 5 gives the r educing power

.
, ,

o f the ore .

PR E LI MI N A R Y ASSA Y No 3 , .

5 gr a m s o f p yr i t o u s o r e 1 2 gr a m s of Na CO , ,

1 00 gr a m s o f Pb O S a lt co ver

It will b e no ted th a t the redu cing p o wer of the ore is grea ter
th a n th a t obt a ined in prelimin a r y a ss a y No 1 In o rder t o
d d
. .

etermine t h e r educing pow er o f a rgol a n ch a rco a l m a ke up ,

the following ch a rges in duplic a te

PR E LI MI N A R Y ASSA Y N O 4 ,PR E LI MI N A R Y AS SA Y No 5
.
,
.

5 gr a ms S iO 2
5 gra m s S iO ,

60 g r a m s Pb O 60 gr a m s Pb O
1 0 gr a m s Na CO , , 1 0 gr a m s Na CO , ,

2 gr a m s a r g o l 1 gra m cha r c o a l or co k e o r coa l

Bo r a x gla ss cover dust
B ora x gla ss co ver
T his h
1 f n t p d
as r e er e ce y KN O
o ur e r s.
62 A M A N UAL OF FI R E A SS AYI N G

In order to deter mine the oxidizing po wer of niter as com

p a red t o ch a rco a l m a ke u p the follo wing ch a rge in du p lic a te :
,

PR E LI MIN A R Y ASSA Y , No . 6
5 gra ms SiO,
1 g r a m ch a r coa l, et c .

60 gra m s Ph O 3 g ra m s K NO,
1 0 g ra ms Na , CO, Bor a x gla ss co ver

Ca lcul a te results a s directed for niter i n pyritous ores .

Ce r t a in b a sic ores will h a ve a n a ppreci a ble oxidizing power ,

so th a t when the usu a l a mount of reducing a gent is a dded t o the

ch a rge to obt a in a 20 gr a m l ea d button it is found th a t due t o

-
, ,

the o x idizing p ower of the ore the button is deficient in size

, .

The o xidizing ingredi ents of a n ore a r e gener a lly hem a tite

m a gnetite d
a n m a ng a nese o x id es ; e g MnO, The r ea c . .
,
.

t ion which t a kes pl a ce is a s foll ows

2Fe, O, C 4FeO CO,

One gr a m of Fe, O, requires gra m of c a rb o n to reduce

it to FeO .

In order to determine the oxidizing power of a n o r e m a ke u p ,

the following ch a rge if the ore consists mostly of b ase When

,
.

consid er a ble silic a is present in the or e de cre a se th e silic a i n the

,

ch a rge :
1 a ssa y t o n o f o r e 15 g r a m s S iO ,

20 gra m s Na CO z , 1 5 gr a m s co a l
90 gr a m s Pb O Bora x gla ss co ver
 CHA PT E R VI

T HE C R UC I BL E ASS A Y ; AS S A Y S L A GS

d
In a lmost every inst a nce when a crucible a ss a y is to be m a de
, ,

t h e ore a n the fluxe s a dded a r e thoroughly incorpor a ted by

dd
mixing so th a t theoretic a lly a t l ea st every p a rticle o f the o re
, , ,

~
is in cont a ct with a p a rticle o r p a rti cl e s of fl ux es an r e rrcing ‘

a gent the most f a vor a ble c o ndition t o pro duce a thorough re a o

,

ti o n a mong th em The sep a r a ti o n of the precious met a ls is

.

dependent up o n th eir a ffinity fo r met a llic l ea d fo rming a n a ll o y

d
,

o f le a d go ld a n silv er in which l ea d gre a tly prep o ndera tes

d
, , ,

which re a dily settl es by gr a vity from the b a l a nce of the

d
an

o re a n flu x es which h a ve united to form a sl a g The ore to be .

a ss a yed must in a ll inst a nces b e in a finely crushed condition ,

v a rying in A meric a n pr a ctice from 8 0 mesh up to 200 mesh

-
,
-

m a teri a l Wh a t t a kes pl a ce within the crucible depend s up o n

.

so me or a ll of t h e f o llowing f a ct o rs
'

1 The finen ess of c r ushing A r e a ll the p a rticle s of go ld

d
. .

an silver or th eir a ll o y p resent entirely set free from the in ,

closing g a ngue ? In some o res this t a kes pl a ce with much co a rser

crushing th a n in o th ers In oth er o res the m et a ls a r e so finely
.

dissemin a ted th a t a ll a re no t set free within the limit sof c r ushing

d
a s c a rr ied out .

2 The mod e of occurrence of the gold a n silver

. Is it in .

the free st a te a s is m o st gener a lly the c ase with gold or a re the

, ,

precio us met a ls in the form of a more or l ess complex mi nera l

compound (t ell urid es a rgentite which must be deco mp osed
d
, ,

before the gold a n silver will a ll o y with the le a d ?

3 The physic a l properties of the sl a g produced ; e g
. its . .
,

fo rm a tio n point its fluidity a t temper a tures somewh a t a bove its

d
,

fo rm a tion p oint a n i t s fluidity a fter superhe a ting

,
.

4 The chemic al n a ture of the sl a g its a cidity o r b asicity

.
, ,

the n a ture of the b ases present more p a r ticul a r ly co p per zinc

, , ,

a ntimony m a ng a nese iron etc

d
.
, , ,

If a crucible be broken open a n its content s ex a mined shortly

a fter fu si o n h a s c o mmenced these will be found to co nsi st of a
,

63
64 A M A N UAL OF FI RE A SS AYIN G

d
h eterogeneous m a ss through which a r e sc a ttered innumera bl e
p a rticl es of lea d both micro sc o pic a n m a cro sc o pic The l a rger
,
.

p a rticles h a ve been fo rmed by the co a lesc ence o f the sm a ller p a r

t icles gr a du a lly settling thro ugh the ch a rge t o w a rd the b o tt o m

d
o f the crucible t o form the fin a l le a d butt o n a s t h e temper a ture

r ises a n the ch a rge b ecom es more fluid a n less resist a nt It is d .

evident th a t t h e completeness o f the c o llection o f the precious

met a ls d epends upon the m a in f a ctors a lre a dy outlined The .

temper a ture a t which c a rb o n b egins t o rea ct with Pb O to form

Pb is 53 0 to 555 C well bel o w 88 4 C t h e m elting-point of Pb O
l °
.
,
°
.
,
.

The form a tion p o int o f a b o ra te silic a te Pb O Na , O 4 S iO, 2 B , O8 , , , ,

( S eger Cone N o the constituents

. of which a re cont a ined
in ne a rly a ll a ss a y ch a rges is 59 0 C ,
°
.

In the f usi o n o f a m ixture cont a ining silic a v a ri o us b a s es

d
,

bora x gl a ss th a t S ilic a te b o r a te h a ving the l o west form a ti o n

d
an ,
-

p o int will fo rm a n th en a s the temp er a ture rises a bs o rb eith er

,

silic a o r b a se o r b o th a s these a r e in exc ess o f the r a ti o required

,

to form the l o west fo rm a ti o n p o int c o m p o und If the temp er -

.

a ture d o es no t rise high enough t o c a use this a bs o rpti o n the ,

e x cess of silic a o r b a se o r b o th w ill rem a in in susp ensi o n in the

f o rmed silic a te b o ra t e pra ctic a lly in a n un a ltered c o ndition If
-
, .

t h e formed silic a te et c c o nstitut es the gre a t er p a rt o f t h e m a ss

,
.
, ,

there will be a n i m pe r fect no n h o m o gen eous sl a g ; if t h e e x c ess -

o f silic a or b a se f o r m s t h e g rea t er p a rt o f the m a t er i a l th ere will ,

b e a slightly fritt ed m a ss
d
.

T a king the simplest c a se a n a lso the most un co mm o n th a t of , ,

a n ore cont a ining f r ee g o ld c o m pl et ely lib er a t ed by c r ushing the ,

p a rticle o f le a d fo rmed a t a c o mp a r a tiv el y low temp era ture ca n

2
, ,

unite a t o nc e a s soo n a s fo rm ed with the gold p a rt icl e not in

d
, ,

cl o sed in g a ngu e a n c o mmenc e settling t o t h e b o tt o m t o form the

l ea d button It is evid ent th a t in this inst a nc e t h e h o m o geneo u s
d
.

fusi o n a n ch em ic a l d ecomp o siti o n of the o re a r e imm a teri a l .

T a king however t h e f a r m o r e comm o n c a se in whi ch the met a ls

, , ,

a r e no t co m pl etely lib er a t ed by crushing it is evid ent th a t the ,

p a rticle of go ld still in cl o s ed wi t hin the g a ngue c a nn ot b e rea c he d

by the l ea d a lre a dy r edu ced ,a n it b ec o m es p r a ctic a lly essenti a l d
to hold the l ea d in pl a ce until the o re p a rticle c o nt a ining the gold
1 D oeltz d
un G r a u m a nn, M eta ll ur g i e, I V , 420 . d
A c cor ing to R o sc oe a n dS ch o r lem m er ,
T r ea t ise on Ch emistr y , II , 865 CO r e a c ts w i th Ph o t o o r m Pb , f a t 1 00
°
C H .

f M o sto w i tsc h M eta ll ur g ie IV

d
w i th PhO to or m

dp
r ea c ts Pb at 3 10
°
C
.
, , , 648 .

pr ob a bly be m a ny pa r ticles pr esent

d d
3
T h er e w ill of l ea for each g ol ar tic le . so th a t
no g ol will esc a pe fo r la c k of lea .
66 A M A N UAL OF FI RE ASSAYIN G

d
d
solid solution Boric a cid a n a lk a line b o ra tes a ct simil a rly
.

t o silic a a n if bor a x is used in the fusion the fin a l sl a g will be

d
,
”
a comple x solid solution of silic a tes a n bora tes of Pb O
d
.

N a , O FeO Ca O etc d ependent upon the b a ses in the o r e a n

, , ,
.
,

the fluxes used .

S ilic a tes a r e defined in d egree by the r a tio of oxygen in the

b a se to tha t in the a cid The chemic a l cl a ssific a tion is a s follows :
.

T A B LE V .
— S I L I CATE DE G R E E S

Mg O FeO S iO, . .

Mg O Ca O 2S iO, . .

Ca O 2 S iO, .

The met al lurgic a l cl a ssific a tio n is m a d e o n the s a me b a sis ,

i s o x yge n in the b a se to th a t in t h e a cid but is somewh a t

. .
, ,

diff erent It is the o ne a do pted in these notes

. .

T A B L E V I — S I L I C AT E D E G R E E S
.

N a me Fo r m u la , R 20 , (b a se)

Bor a tes m a y b e cl a ssified in a somewh a t simil a r m a nner .

In gener al , it m a y be st a t edth a t the higher the silic a t e d eg r ee

d
,

the m o re infusible is the mi xture a n th a t a polyb a sic mi x ture , ,

one of m a ny b a ses is mor e e a sily fusible th a n one of few These

,
.

general st a tements a re not with o ut e x ceptions for cert a in b i

d
,

silic a tes a n t risilica t es h a ve a l o wer fusing p o int th a n the c o r re

d
d
sp o n ing mon o silic a t e etc It a ls o depends grea tly U p o n the
,
.

b a se wh a t the fusibility of the silic a tes will be Ph O Na 20 a n .

, ,
 T HE CRUC IB LE ASSAY 67

K , O give sily fusible silic a tes ; FeO a n MnO g ive comp a r a d

d d
ea

t iv ely r ea dily fusibl e silic a t es ; A 12 0 ,” Ca O a n Mg O give iffi

’

c u lt ly fusibl e silic a t es Wh en h o wever silic a tes o f a ll t hese v a r i

d
.
, ,

o u s b a ses a r e mi x ed a n g o into s o luti o n a s a h o m o g en eo us m a ss ,

t h e e ff e c t o f this mi x ture o n the melting point o f the m a ss is -

o ften t o l o w er it In f a ct the silic a t e mixtures a r e to be l o o ked

.
,

up o n fro m t h e s a me p oint of view a s met a llic a llo ys ; th ere m a y

be eutectic mixtures i e mi x tures of two or more c o nstitu ents ,
. .
,

which h a ve a l o wer m elting p oint th a n eith er of the co nst it u t ent s

-
,

a s is illust r a t ed in the a cc o mp a nying di a gr a m

1
.

d
R h o o ni t e Hyper s t h e ne
2 ( Fe O) 2 ( S 1 O, )
2 (M n 0 ) 2 ( S i 0 3 )

Hyp er sth ene

Rho dion te

FI G . 46 — FR E E z I N G p o I N T
.
-
CUR VE ; R HO O D NI T
E —H Y PE RS TH E N E .

T he u t ec t i c mi x ture o r t h e c o mp o siti o n of l o west m elting

e ,

p o int in t h e s er i es o ccu r s a t 20 p er c ent hyp ers t h ene (t h e

d
-
.

bisilic a t e o f i r o n) a n 8 0 p er c ent r h o d o nite (t h e bisilic a te o f .

m a ng a n ese) T h e m elt ing p oint o f this m i x ture is 98 5 C

. e
°
.
,

which is c o nsid er a bly l o wer th a n th a t of eith er c o nstitu ent

a l o ne .In the s er i es Ca S iO,, Na 2S iO3 a minimu m Oc cu r s in
—

t e freezing p o int curv e a t a c o mp o siti o n of 8 0 p er cent N a , S iOs

h
d
- .

20 p er c ent Ca S iOs t h e f r e ezing t emp er a ture b eing 9 20 C

d
°
an .
,
.

while the f r eezing p oint of N a 28 i0 3 is a bo ut 1 0 1 0 C a n th a t °

.

o f Ca siO8 is 1 505 C 2 °
.

T yp i ca l A ssa y S la g s —
A S l a g of lo w f o rm a ti o n temp er a ture
d
.

an c o nsid er a bl e vis c o sity a t th a t te m per a ture c o rrespo nds t o

S eger Co n e No . 590 C This °
.

m a y b e writ t en :
1 J . H L Vog t
. .
, D e S il ika t sch mel z l osu ng en, II , Ch risti a na .

2
R . C . W a ll a c e , Z ei t A no r a Ch em
. . . L XIII . 2
68 A M A N UAL OF FI RE A S SAY IN G

c al c ul a tion from the

By at omic weights the following ch a rge
will yield this sl a g
Pb O . gr a m s
S iO, I gr a ms
gr a ms
The sl a g corresponding t o S eger Cone an, melting a t d
740 C m a y be desira ble for a luminous ores
°
.
,

which m a y be written (Na z B,

O, Pb O A 12 0 3
. . .

The foll o wing ch a rge will yield this sl a g

Ne zB , O, .
g r a ms A 120 8
Pho 24 9 gra ms S iO,

TA B L E V II — . ASS A Y S LAG S 1

F or mul a R ma r ks
e

1 . 2 Na zO Si Oz
. Mo nosilic a te . . Vit r eo us , co lo r less , tr a ns
pa r ent .

2 . B isili c a te S to ny w hi te
, , c r y s ta l

line .

3 2Pb O S iOz
. . Monosilica te . . Vit r eo us , lig h t yell o w ,

tr a ns p a r ent .

4 PbO S iOz
. . Bisilica te . Vi t reo us, lig h t yellow ,

V y fl idt ny bl k
tr a nsp a r ent .

5 N3 20 F0 0 S i0 2
. . . Monosilica te . er u , s o ac .

6 Na zO FeO 2 S iO
. . . Bisilica te Vit bl k
reous , ac .

7 PbO FeO S iOz

. . . Monosilic a t e . . R in b l k
es o us , ac .

8 Na aO PbO S iOz
. . . Monosilic a t e . Vit y ll w g n
r eo us, e o - r ee .

9 N a zO PbO 28 iOz
. . . Bisilica t e Vit y ll w-g n
r eo us , e o r ee .

10 . Mo nosilic a te . Vi t u bl k
reo s, ac .

11 . Mo nosilica te . . Vit bl k n
r eous , ac , co

t ai ns ysta ls
sq . cr .

12 . Bisilica t e Vitr eo us bla ck , .

13 . Mo nosilic a te . . S to ny lig h t yell o w

, .

14 . M ono silic a t e . . Viscous sto ny g r ay , ,

brown .

15 . Monosilic a te . V itr eo us, b la c k .

p a rti a l repl a cement of t h e S il ic a by bor a x gl a ss in t h e

A
foregoing S l a gs will a ppreci a bly l o wer the fo rm a tion points
d
.

B a ses such a s FeO Ca O Mg O MnO Ba O a n A 12 0 3 a r e

d
, , , , ,

p resent in grea ter or lesser qu a ntity in a lmost a ll ores a n S iO, ,

is p resent in pra ctic a lly every o re so th a t such S l a gs a s those ,

W
es t , La b or a t or y , S D S c h oo l

d d
1 El m er E . . . of Mines 1 90 4 ,

S tony S lag s in ic a te inco mplete so lu ti on o f so me o f th e ing r e ients .

 T HE CRUC I B LE AS SAY 69

outlined must necess a rily be m a de The e a sily fusible b a ses

d
.

Pb O a n Na , O serve t o l o wer the f o rm a tion p o int of the sl a g .

If it is a ccepted th a t the comp o sition of the sl a g in the a ss a y is

pr a ctic a lly the const a nt f a ctor it is evident th a t when the a p
d
d
,

proxim a te comp o sition o f the ore is kno wn we will a either ,

'

b a sic or a cid fluxes in such propo r tions a s to produce the p roper

,

sl a g decided upon The most d esira ble co nstituti o n for a n a ss a y

.

sl a g in gener a l is th a t of a monosilic a te or a sesquisilic a te some

, ,

times but more r a rely a bisilic a te If the ore is b a sic a bisilic a te

, ,
.

m a y be a ppro a ched if a cid a monosilic a te o r even a sub silic a te

,
-
, ,

in o rder to insure complete decompositi o n of the ore .

The a ccomp a nying t a ble will sim p l ify sl a g c a lcul a tions

TA B LE V I II .
— T HE CAL C U LATI ON OF S LAG S 1

UN I T MOL E C ULA R B A S E R A TI O ; E G . .
, PB O: NA ,,O : FE O, ET C .
=-
1: 1 : 1

Pa rt s of o th er ba ses necessa r y

One pa r t by w eight of Na , 0 Pb O Ca O A l, 0 , FeO Zu o Cu O

S iO, req ui res t o fo r m
th e m o no si li ca te p a rt s pa rts pa rt s pa rt s par ts pa r ts p a rt s

When a bisilic a te is t o be c a lc ul a ted the silic a required for

d
,

a monosilic a te is dete rmi ned a n then multiplied by t w o Vi ce .

d
versa when the b a ses for the m o nosilic a te h a ve been c a lcul a ted
,

an a bisilic a te is to be formed the b a ses must be divided b y ,

‘

two The sa me re a soning a pplies t o other silic a te degrees

. .

1 B a se d
on B a lling
’
s ta ble .
70 A M A N UAL OF FI RE ASSAYIN G

E x a mp le f o the Ca lcula tion

f The pro blem
o is a n A ssa y S la g .
—

t o c a lc ul a te a ch a rge to pro duce the f o ll o wing monosili c a te :

N T a king a s the unit 1 0 gr a ms o f
N a , O it follows from t h e prec eding t a ble th a t the weights of the
,

subst a nces required a re :

Na , O 10 X 1 gr a m s
Pb O 1 OX 3 59 . gr a m s
Feo 10 X 1 1 6 . gr a m s
1 0 X 0 903 =
. g r a ms
The silic a required will be
for th e Na , 0 10 gra ms
Pb O gr a m s
FeO gra ms
Ca O gr a m s

Tot a l gra ms S io
d
,

The silic a m a y b e et ermined by c a lcul a ting it fo r o ne b a se

an d mul t iplying th a t figure by the numb er o f o xygen m ol ecul es
in t h e b a ses present a ft er h a ving reduc ed the sl a g fo rmul a t o its
,

l o west possible terms Bef o r e m a king up t h e c h a rg e it is

.
,

ess enti al to rememb er th a t the N a , O in this inst a nce is furnish ed

in the form of N a HCOs whi c h cont a ins a ppro x im a tely 4 0 p er
d
,

c ent o f N a , O a n th a t t h e FeO is furnished by a n iro n o re o f

.
,

t h e f oll o wing a ppro x im a te c o mp o siti o n

Fe, O, 8 0 p er c ent ; S iO 1 7 p er c ent

,
. .

The lime is furnished by li m esto ne Ca CO,” pra cti c a lly pure ,

.

It is a lso n ec ess a r y t o pro vid e a le a d butt o n ; so ex tr a lith a rge

must be fu r nish ed T o reduce t h e l ea d c o a l dust is a dd ed
.
,
.

S o m e o f the co a l will b e us ed up t o reduce t h e FezO, t o FeO .

H ence t h e foll o wing c a l c ul a ti o ns a r e to be m a de : 1 0 gr a m s N a zO

10
a re required ; th er efo r e X I OO= 25 g r a ms of Na HCO, must
ZO
be a dd ed . Pb O cont a ins 92 per cent . of Pb ; the r efo re in o rd er ,

20 >< I OO
to o bt a in a 20- gr a m le a d butto n ,
—
22 gr a ms of Pb O
92
must be a dded in a ddition t o the gra m s fo r the silic a te
d
,

a to t a l o f gra ms of Pb O E l even a n six tenths gr a ms o f

.
-

FeO a r e r equi r ed Fe, Oa consists o f 9 0 per cent of FeO a u l

. per .

cent of . 0 an d the ore is

as 80 per cent of . FezOm
g o x 80
X 1 00
 T HE CRUC IB LE A SS AY

g r a ms of or e will be required . The limestone cont a ins 54

X 1 00
per cent . Ca O; therefo re , gra ms of limestone
54
w ill be required .

The c o a l in use h a s a reduci ng power of 20 g r a ms of le a d per

d
gr a m of c o a l .

The foll o wi ng re a c t i o n t a kes pl a ce between c a rbon a n t h e

Fe, Os .

2Fe , Oa C 4FeO CO, .

12
One gr a m of Fe, Os requires g r a m of ch a rco a l
32 0
.

Bu t as the co a l use Is only d 20 X 1 00

58 per cent . as stro ng as

ch a rc o a l the following qu a ntity will h a ve

,
to be a dded to the
gr a ms o f Fe,,O8 t o reduce it
X X 80
gra m co a l .

To this must be a dded 1 gr a m for the reduction of the g r a m 20-

le a d butto n giving gr a ms o f c o a l t o be a dded

,
.

S ince the I ro n o r e c o nt a ins silic a this Is to be deducted from ,

t h e silic a c a lcul a ted The a mount o f S iO, in the ore is 16 1 x 1 7

. .

p er cent . gr a ms .

The correct ch a r ge then is

Na HCO, gr a m s . . li mestone
Ph O gr a m s . . silica
. Fe , O, (i r o n o re ) 1 82 . gr a m s
. . c oa l

S a lt c o ver

F ollowing is the c a lcul a tion of the s a me sl a g but for a qu a rt z ,

o r e cont ai ni ng 95 per cent S iO, The formul a for the sl a g is : . .

N T a king a s t h e u ni t 1 a ssa y to n o f
o r e or in round numb ers 30 gr a ms this will cont a in
, ,
gr a ms
, ,

o f S iO, These
. gr a ms a r e to be divided into 4 equ a l p a rts
t o s a tisfy the 4 b a ses present Therefore gra ms of S iO2 .
,

will go to such a n a mount of e a ch b a se a s will form a mono sil ic a te .

7 1 gr a ms S io , r e q u ir e X 2 07 . gr a ms Na O ,

7 1 . g r a m s S iO , r eq u ir e gr a m s Pb O
7 1 g ra ms S io ,
-
. r equ i r e 7 . 1 gr ams FeO
7 1 gr a m s S iO2
. r eq u i r e 7 . 1X gra m s Ca O
72 A M A N UAL OF FI RE ASSAYIN G

X 1 00
The bic a rbon a te of s o d a required is 37 gr a ms .

40
T h e Pb O requi r ed is g r a ms including the
l ea d butt o n .

The FeCO, (sid erit e) required is 27 gra ms .

The lim est o n e required is gr a ms .

T he compl ete ch a rge is :

l a ssa y to n ore 27
37 gr a m s
74 gr a m s 1 gra m
S a lt c o ver

In one c a se the o r e is o f a b a sic n a tur h em a tite a n lim e — d

d
e

st o n e ( 1 7 gr a ms of e a ch) a n in the other c a se it is of a n a cid

,

u a r t z ; yet t h e sl a g pr o duc ed is the s a me in b o th

d
na t u r H
c a s es This brings out the f a ct th a t the sl a g is the c o nst a nt a n
d
.

th a t flu x es a r e a dded of such n a ture a n in such qu a ntity d et er ,

mined by the ore a s to produce a sl a g of f a irly const a nt comp o si

,

ti o n It is to be n o t ed th a t the sl a g m a de i n t h e two a ss a ys
d
.

c o nt a ins fo ur b a ses Pb O N a zO FeO Ca O a n th a t these a r e

, , , , ,

present in unit m ol ecul a r b a se r a ti o A s a m a tt er of f a ct the .

,

a ss a y er r a rely a dds Ca O or FeO a s flu x es but when these a re ,

present in the sl a g th ey a re d erived fro m the o r e The b a ses

d
.
,

a dded a s flu x es a r e pr a ctic a lly limited to three Pb O N a zO a n , , ,

a t times K, O so th a t when a n o r e c o nsisting chiefly of S iO, is

d
, ,

t o be a ss a y ed t h e sl a g m a de will a pproxim a te a mon o silic a te a n

d
,

b o r a te o f le a d oxide a n s o d a .

The t a bl e o f a ss a y S l a gs given mentions o nl y those in which

the b a ses a r e present in t h e unit mol ecul a r r a ti o It is evid ent .

th a t wh ere a n ore is consid ered in which numero us b a ses a r e

p resent these
, a r e no t c o nt a in ed in the un i t m o l e cul a r r a ti o so ,

t h a t the formul a of the sl a g m a de will r a ther h a ve this gen er a l

fo rm
( X Pb O y N a z O zFe O t M ,
O
g ) v S i0 2 , , ,

in which fo r a monosilic a te c o nsid ering the letters a s oxygen

, ,

coe ffi ci ents ,

In order t o get a sl a g of low fo r
m a ti o n p o int the coefli cient s of the m o re inf usible b a ses such
, ,

a s Ca O Mg O A 12 0 ,” will h a v e to be m a teri a lly sm a ll er th a n th o se

, ,

of the m o re fusibl e b a ses Pb O N a zO a n FeO , , ,

d .
74 A M A N UAL OF FI R E ASSAYIN G
TA B L E X I — HE MAT IT E TA B LE XII .
— L I ME STONE
An ly i
a s s of a Hem a ti te A na l ysis o f a Lim esto ne

xid
S ilica
df
p er c ent . .

p er c ent . A lu m ina an err ic o e . .

p er c ent . M ag nesia
Lim e
xi d d
p er cent . .
l

M a ng a no us o e . 0 19
.
p er cent . 1 Ca r b o nic a ci

p
Ph os h or u s p er c e nt . W a t er

These a n a lyses given to sh o w wh a t t h e chi ef b a se co nst it

d
a re

u ent s m a y b e a n h o w o res will r a nge fro m a cid typ es to b a sic

,

d
o nes Wh enever sulphides a r e present it is to be noted th a t the
.
,

o x id a ti o n o f th ese l ea ves b a sic o x id es t o be flu x e

d
.

A t tim es inste a d o f silic a te a n b o r a te S l a gs it is d esir a bl e t o

, ,

m a ke oxid e S l a gs in t h e crucibl e a ss a y This of c o urse ca n o nly .

, ,

be done when silic a is a bsent from t h e ores or wh en a very l a rge ,

e x cess of lith a rge is used in the fusi o n Lith a rg e which melts .

,

a t 884 C p o ssesses t h e pro p er ty of disso lving o r h o lding in

°
.
,

suspensi o n c er t a in qu a ntities of o ther m et a llic o x id es Th ese .

S l a gs a r e discussed in the ch a pter A ss a y of Impure Ores

d
.

T h e ch a rge fo r t h e m o n o silic a te o f l ea d a n s o d a is (using the

unit m ol ecul a r b a s e r a ti o)
0 5 a ssa y t o n si li ca o r qu a r t z o re
39 gra m s Na HCO ,

55 gr a m s Pho
B or a x gla ss co ver
Fo r t he bisilic a te it is
0 5 a ssa y to n si li ca o r q ua r t z ore
20 gr a m s Na HCO ,

28 gr a m s Pb O
B or a x gla ss co ver
A ll o wing f o r a 20 gr a m le a d butt o n t h e ch a rges a re
-
,

No 1 , . Mono si lica te No 2 ,
. quisilica te ( a pp r ox i
ses n
o r e (q ua r t z ) , m a te ) o r e ( qu a rt z ) ,

0 5 a ssa y t o n
. 0 5 a ssa y t on

. 26 gr a m s Na zCO, 20 g r a m s . 14 gr a m s .

Pb O 7 7 gr m s Pb O 60 gr a m s Pb O 50 gra m s
a . . . .

Co a l . 1 gr a m Co a l 1 g ra m Co a l . . 1 gr a m
Bor a x gla ss co ver B ora x gla ss c o ver B or a x gla ss co ver
 T HE CRUC IB LE ASSAY 75

A ll of the a bove ch a rges will yield s a tisf a ctory S l a g s in a n

o r e a ss a y if the ore is of the n a ture describ ed No 3 is the
che a p est in p o int of c o st ; N o 2 is the one m
. .

. ost frequently m a de .

Color of S la g s.
— Mo st S l a gs fro m ore a ss a ys will be fro m
light t o very d a rk green in c ol o r o r a lm o st bl a ck this c ol o r being
,

due t o v a ri o us pro p o rti o ns of ferro us silic a te When iron is

.

a bsent the c o lor of le a d silic a tes (yell o w) m a y predomin a te or

d
, ,

white a n gr a y o r col o rless S l a gs due t o silic a tes of Ca O Mg O Z nO

, , , ,

etc be pro duced Copper produces red S l a gs due t o cuprous

.
,
.
,

S ilic a te. Cob al t gives b lu e S l a gs When much lime is present

.

in a n o r e this is best c a lcul a ted to a bisilic a te or even higher

, ,

while the o ther b a ses ca n be c a lcul a ted t o t h e monosilic a te .

 CHAPT E R V II

C UPE LL AT I ON
Cu pell a tion h a s for its o bj ect the o x id a tion of the le a d in
the gold silver etc a ll o y t o Pb O which in p a rt cent )
d
, ,
.
, p er ,
.

is a bso rbed by the cupel a n in p a rt per cent ) v ol a tiliz ed

d
. .
,

The silver a n gold of the a lloy a r e left a s a met a ll ic be a d The .

proc ess is c a rried ou t in cup els Cupels a r e sh a llow p o rous dish es

.
,

m a de general ly of bone a sh or m a gnesi a produc ed by c a lcining

-
, ,

m a gnesite P o rtl a nd cem ent m a y be used a s a cupel m a teri a l

d
. .

d
Le a ched wo o d a shes (p a rt ic ul a rly from beech w oo d ) a n lime
- -

m a gnesi a h a ve al so been used fo r cupels A mixture o f

d
an .

bone a sh a n l ea ched w o od a shes in the propo rti o n o f 1 t o 2

d d
- -
,

an 2 to 1 respectively h a s been used a n is s a id to giv e a much

, ,

sm a ller a bsorpti o n o f the preci o us met a ls th a n b o ne a sh cup els

1 - .

Bone A sh Cu p els — The b o ne which yi elds the bone a sh o n

.
-

c a lci ni ng h a s the following c o mposition z

.

S heep bo nes Ca tt le bones

p er c ent .
p er cent .

Ca CO, p er c ent .
p er cent .

p er c ent .
p er c ent .

Ca F, p er c ent .
p er c ent .

Or ga ni c ma t t er per c ent .
p er cent .

These bones will pr oduce bone -a s h of the following com position

No 2
.

p er c ent .
p er cent .

p er c ent .
per c ent .

p er c ent .
p er cent .

r c ent p er c ent
p e . .

Ker i P r ob ir Ku nst 1 886 p 9 1

d
1
, , , . .

1 Kemta . E r ma n s J our fa r P Chen

’
. .
, X L VIII , 24 .

76
 CU P ELLATI O N 77

The bone h used fo r cupels must be speci a lly tre a ted b y

-a s

w a shing with a n a queous solution of a mmo ni um chloride (this

s a lt to the e x tent of 2 per cent of the weight of the bone-a sh to
d
.

be tre a ted) 1
This re a cts with Ca CO3 a n a ny Ca O present con
.
,

ver ting them int o Ca Cl , whi ch is remo ved by w a shing with w a t er , .

The presence o f Ca CO3 is very undesir a ble in b o ne-a sh for cupels ,

as it b egins t o giv e o ff CO2 a t 8 00 C a b o ut the tem p er a ture o f

°
.
,

the beginning of cup ell a ti o n c a using a serious spitting of the l ea d ,

button which ent a ils a l o ss of the preci o us m et a ls Cup els should

, .

not be kept whe r e t h e ni t r ous fumes from p a rting ca n be a bsorbed

by them a s the se will form ,
with a ny Ca O th a t m a y
be present which a ls o is decomp o sed a b o ut t h e temper a ture of
,

cupell a ti o n Bo ne a sh melt s a t a bout 1 4 50 C ( H emp el)

.
- °
. .

The physic al n a ture of the cupel especi a lly a s r eg a rds poro sity
d
, ,

is very import a nt F or this re a s o n there should be a c a reful a

.

j ustment o f t h e rel a tive a m o unts o f di ff erent sized p a rticles

present Pr a ctic a lly o nl y the fr a ction of 1 p er cent of the
.
, .

bone a sh should rem a in o n a 3 0 mesh screen If there is a n

- -
.

insu fficiency of fine p a rticles in t h e bone a sh the cupel will be

d d
-
,

t o op o ro us a n c a use a rel a tively h ea vy a bsorption o f go ld a n

silver If the b o ne a sh is too fine the cup els m a d e fro m it will
d
-
.
,

be t o o dense prolonging the cupell a ti o n a n c a using loss es

, ,

m a i nl y by increa sed v ol a tiliz a ti o n .

The following is a screen a n a lysis of the bone a sh c o mm o nly -

purch a sed but which is r a ther co a r se z

, .

Th r ou gh a 20-mesh scr een, 1 00 per c ent .

On a 3 0m esh
- sc r een, p e r c ent .

On a 4 0-m esh scr een, p er c ent .

On a 60-m esh scr een, p er c ent .

On a 80-m esh scr een, p er c ent .

On a 1 00 m esh
- sc r een, p er c ent .

Th r ough a 1 00-mesh scr een, 68 88 per . c ent .

should be a s u ni fo rm a s p ossible a s reg a rds d ensity

Cupels
d
,

a n for this re a son a r e best m a de by m a chine in which a c o nst a nt ,

pressure m a y b e obt a ined r a ther th a n by h a nd m olds Fig 4 7 ,

. .

shows a go od type o f cup el m a chine Conside r a ble pressure m a y

d
.

be used a n t h e cup els m a de quite firm

,
It is not p ossibl e to .

sp ecify the prop er c o nditi o n in d efinite t erms but a b a tch o f

d
,

cupels a fter b eing m a de u p a n c a r efully d r ied for a t le a st th r ee

,

weeks or a m o nth sh o uld be tested by cupeling a weighed qu a n

,

1
W . B et te!. P r oc Ch em . . an d
M et . S ec . of S A
. .
. II , 5 99 .
78 A M A N UAL OF FI RE ASSAYIN G

t ity mgs ) o f c p silver with 20 gra ms o f le a d a t t he pro per

d
( 00
2 . . .

t em p er a ture 8 50 C a n t h e l o ss no ted It sh o uld no t e x ce ed

,
°
.
,
.

from to per cent .

The b o ne-a sh to b e m a d e int o cupels is mi x e d wi t h fro m 8 t o

1 2 p er c ent of w a t er in which is diss o lved a littl e K zCO o r t o
.
,

d
whic h h a s b een a dd ed a li t tl e m ol a ss es o r st a l e b eer A ft er .

m a king the cupels should be c a refully a n slowly dried If

,
.

FI G . 47 .
— CU PE L MA CHI NE .

p o ss ibl e cup els S h o uld b e sever a l m o n t hs o l b efo re u sing In d

d
.
,

t h e R o y a l Br i t ish Mint no cup el s l ess th a n t w o yea rs ol a re

u sed fo r bulli o n a ss a ys .

d d
If cup els a re t o o r a pidly dri ed o r h a v e b een m a d e up t o o w et, .
,

t h ey cr a ck a n c h eck wh en pl a c ed in t h e furn a ce a n m a k e t h e
a ssa ys c o nduc t ed in th em un r eli a bl e .

T h e i m p o rt a nc e o f goo d c up els c a nn o t be o v er esti m a t ed

d
.

V ery frequ entl y in a c c u r a ci es in t h e a ss a ys a r e u e chi efly t o t h e

,

cup el T h e sh a p e o f t h e cup el h a s s o m e influ en ce o n t h e l o ss o f

d
.

p r eci o us m et a ls by a bs o r pti o n If t h e cup el is v er y fla t a n

d
.

sh a ll o w ,
so th a t t h e m o l t en l e a d c o v er s a l a r ge a rea a n has
lit tl e d epth t h e ti m e o f cup ell a ti o n is d ecrea sed a s the surf a ce
,
 CU P ELLAT I O N

ex posed t o o x id a ti o n is increa sed but a s the a bso rption of preciou s ,

met a ls is pro b a bly a functi o n o f the a rea ex posed it will be l a rge ,

in sh a ll o w c upels 1
.

M a g nesia Cu p els Of recent yea rs the so c a lled p a tent

d
— - .

cup els h a ve c o m e into wide u se esp eci a lly in E ngl a nd a n S o uth

d
A fric a a n t o a lesser ex t ent in the U nit ed S t a t es These cup els
.

a r e m a de a lm o st inv a ri a bly o f a m a gn esi a b a s e This m a gn esi a .

is pro duced by c a lcining crud e A ustri a n Ca lifo rni a n or Turkish

d
,

m a gnesite a n is used l a rgely in the steel industry for b a sic

,

d
refr a ct o ry brick .

The composi ti o n is a b o u t 90 p er c ent Mg O a n 1 0 per c ent o f

d
.
,

impu riti es chiefly Ca O FezOs A 13 0 , a n S iO, The cupels a r e in

d d
.
, , ,

v a ri a bly very h a rd a n firm o f a bro wn c olor a n a re fo rmed under ,

high pressure The e x a ct c o m positi o n of the cup els is gener a ll y

.

a tr a de secret Ma gnesi a cup els c a nnot very rea dily be m a de in

d
.

the l a b o r a tory like b o ne a sh cupels a n in al m o st a ll inst a nces -

,

th eir c o st is higher A nu m ber of br a nds a r e o n t h e m a rket a s .

,

the Mo rg a nite cupel m a d e by t h e Morg a n Crucible Cc Ba tt erse a

d
,
.
,

Works Lond o n those m a de by Deleu il P a ris a n the Ma b o r

, , , , ,

S c a lit e V elt erit e S t a r et c br a nds

,
Mo rg a nit e cup els
,
mm ,
.
, .
, . .

t o p di a meter (a bout in ) the c o mm o n siz e cost per .

,

1 00 in S t Lo uis . .

The pro pe rties of v a ri o us types of cup els a r e discussed in a

foll o wing secti o n
d
.

P or tla n Cement Cu p els — S a tisf a ct o ry cup els m a y b e m a de .

o f o rdin a ry P o rtl a nd c ement pro vided t h e a mount o f mi x ing

w a ter is c a refully a dj usted 2

The a mo unt of w a ter sh o uld be .

8 per cent of the w eight o f the c em ent

. If l ess th a n 5 p er c ent . .

w a ter is used the cupels a re t o o fra gil e if 20 p er c ent is used t h ey ,

.

will no t re a dily p a ss the cupel m a chine Up o n h ea ting cup els

d
.
,

with less th a n 5 per cent a n with m o re th a n 1 5 p er c ent w a ter

d
. .

cr a cked a b o ut the edges Cup els m a de of o ne h a lf c em ent a n

- .

o ne h a lf b o ne -a sh give g o o d results
-
.

Cement cup els a r e v er y ch ea p a s c o mp a red t o b o ne a sh - .

Cement will c o st fro m 3 5 c ents t o p er 1 0 0 lb while bon e .

a sh costs fro m to p er 1 00 lb C e m e nt c up els sh o uld .

b e th o r o ughly dri ed befo r e u se o th erwis e they will d ev el o p ,

cr a cks during h ea ting .

H K Ed m ndE ng nd M in J LXXX 2 45
T P H lt nd
1

E xp i m nt W i th P tl nd
. . a s, . a . our , .

“
C m nt C p l
2

nd
N C Ch i t n n
nd
. . o a . . E ng r s e se , er e s or a e e u e s, .

J W M
“
M in J B n A h C p l M in ”
a X C 56 0
. o ur it t
.
, C m nt , . . . err , e e vs . o e- s u e s, . a

S ci P r ess C 64 9
.
. . .
80 A M AN U AL OF FI R E A SS A YI N G

CUP E LLA T ION 1

Wh en rea d cu pel lea d
d d m d d
.
-
y t o b u t to ns, t h e cu pels
pl a c e empty in t h e re h ot uffle a n a ll o w e to re m a in
dr
-
a re , ,

there fo r a bout 1 0 minu tes in o r e t o ex pel a ny moist u re o r

d
,

o rg a ni c m a t te r p resen t if m o l h
d
( as b ee n use in
d
a sses w a t er

m a king th em u p)
d
If t h e b u tto ns w ere pla ce into th e col
.

c upel t h e le a w o ul d melt b efo r e a ll the re m a ining m oi stur e is

d
,

expell e w hich wo ul d then p a ss u p vi olent ly t hr o u g h th e molten

,
“
le a d c a using wh a t is te rmed sp itt ing i s t h e p roj ectio n o f
”

d dd
, . .
,

sm a ll le a p a r ticl es ca r r ying gol a n silv er from t h e cu pel

d
, .

S o me cupels m a e fro m b o ne-a sh co nta ining Ca CO, w ill co m

, ,

mence to spit a fter the cupell a ti o n h as p r o c ee ded fo r so m e time

an d the t e m pera ture h a s r isen to a b ove 8 00 C This ca n be °
.

stopped by pull i ng t h e cupel to the coo l e r (f r o nt ) p a r t o f t h e

d
‘

mu m e a lthough the cupell a tion a fter spitti ng is to be co nsi

d
, , ,

ered u nr el i a bl e Wh en a piece of woo d or c o a l is pl a ce in t h e

.

“
mu m e t o o pen up le a d butto ns the cu pels ab sor b gases a t ,

times which l a ter on w hen the tempera ture rises a re a g a in ex

d
, , ,

p e ll e with
,
a spitting o f the le a d .

Wh en the l ea d butto n is put into t h e h ot c u pel t h e le a d

d
,

melts (3 26 C ) a n is c o vered by a g ra y bl a ck scu m If the l e a d

°
.
-
.

butto n is pra ctic a lly pure a s it sh o ul d be th is bl a c k scum dis

, ,

a ppe a r s when the l ea d re a ch es a tempera t ur e of 8 5 0 C Thi s °

.

“ ” “ ”
is c a lled the o pening up o r unc o v er ing of the le a d button
d
.

d
The m olten l ea d th en a ppe a rs bright be g ins to drive a n , ,

ra pid oxid a ti o n comm enc es Le a d butto ns sh o uld

d
a ctive a n .

uncover as so o n a s po ssible in the mu ffle If o ther a n m o re

d
.

iffic ultly fusible met a ls su c h as Cu Fe etc a r e pres ent the

d
.
, , , , ,

temp er a tu r e o f unc o ve r ing is high er a n t h e temper a ture re

quired for cupell a ti o n is higher These fo rei g n met a ls sh o uld .
,

however a s a genera l rul e b e a bsent

, ,
.

Little fl a k es of Pb O fo rm on the su r f a ce of the m o lten l ea d

d
a n slid e down t h e c o nve x surf a c e of the button a n a r e a bsorbed ,
d
by the porous m a ss of the cup el The pro c ess o f cupell a tion is .

dep endent upon the rel a tion of the surf a c e of the cupel t o th a t
of the molten l ea d a ll o y a n the lith a rge which is fo rmed by d
o x id a tion Th ere is a grea t ifler ence between the surf a ce d
d d
.

”
tension of molt en l ea d a n lith a rge a n while lith a rge c a n wet
d
d
the bone a sh surf a ce a n hence be a bso rbed m olten l ea d c a nnot ,

d
do so or onl y t o a very slight ex tent a n hence is not a bso r bed
,
.

In the sa me m a nner met a llic silver a n gold left o n the cupel b y ,

1 T he d esc r i p tion w h ich follow s r ef ers in th e ma in to b one-a sh cu pels .

82 A MA N UAL OF FI RE A SSAY IN G

cu p ell a tion for silver i s c a rried o n the tempera ture should no t ,

be a bove 8 20 C in which c ase c ryst a ls of lith a rge (fe a thers)

°
.
,

form on the si de of the cup el tow a rd the mu m e mouth If the .

tem p er a ture is too low for the cupel to successfully a bsorb

pr a ctic a lly a ll of the Ph O these fe a thers form low down in the ,

cupel When t h e tem p era ture is a b o ut right they form ne a r

.
,

the upper rim of the cu p el It is however to be noted th a t the .

, ,

dra ft through the muffle influences the form a ti on of fe a ther

lith a rge ; i e if the dr a ft is strong fe a thers will fo r m a lthou gh
. .
, , ,

the temper a ture is somewh a t a bove 8 20 C D uring cupell a tio n

d
°
.
,

the do o r of the mu ms should never be left wi de o p en but sh o ul ,

be set slightly a j a r, so th a t the cold air will not strike directly

upon the cupels When silver a n gold a re cupelled for owing
. d ,

to the higher melting p oint of the silver gold a ll o y the finishing

- -
,

t empera ture will h a ve to be 86 0 C a t le ast

°
. .

d
A s the cupell a ti on p roceeds the p ercent a ge of le a d in the
d
,

d
a lloy decre a se s a n th a t of A g a n A u incre ases The lith a rge .

thrown o fl from the center of the button is in l a rger specks a n

d
,

b rilli a nt an the button a ssumes a more rounded form When

,
.

thi s phenomenon a ppe a rs the cupel should be p ushed b a ck into ,

the hotter p a rt of the furn a ce or the tempera ture o f the furn a ce

r a ised somewh a t When the l a st of the Pb goes o fl l a rge buttons
'

.
,

a re covered with a brilli a nt film of colors (inte r ference colors)

d
d
an the button a pp e a rs to revolve a xi a lly The colors then .

dis a ppe a r the be a d becomes d ull a n then a g a in t a ke s on a

, ,

silvery tinge .

If new the temper a ture of the mu m e i s bel o w th a t of the

melting point of silver (96 2
- °
or below th a t of the gold silver -

a lloy constituting the be a d or if the cupel be withdr a wn from ,

“ ” “
the furn a ce the blick or brightening or fl a sh o f the” “ ”
,

be a d t a kes pl a ce ; i a the be a d suddenl y becomes very bright

. .
, ,

a t the moment of solidific a tion owing to the rele a se o f the l a tent ,

h ea t of fusion which r a ises the t emper a ture of th e be a d very

d
,

much for a short time The h ea h as been in a st a t e of surfusi o n

.
,

i e in a st a te of fusion below its true freezing point t o w a rd

d
.
-
,
.
,

the l a st o f the cupelling oper a ti o n ; a n if it be lightly j a rred or the

temper a ture a llowed to dro p still l o wer (by t a king it o u t of the
mu ffl e) it suddenly conge a ls a n a ssumes a st a te norm a l (solid)
, d
to the tempera ture existing The rele a se of the l a tent he a t .
,

r a ising the tem p er a ture of the be a d c a uses t h e brightening ,

.

“ ”
The brightening of very sm a ll be a ds is ra rely notic ea ble .
 CU PE L LA T I ON

S ilv er d
g ld be ds still c nt ining sm
l a m o unts of Pb o r Cu al

d
an o a o a

o no t bright en so n o tic ea bly If even minute qu a ntities o f .

r h o diu m iridiu m ruth enium osmium or o smium iridiu m a r e

d
-
, , , , ,

present butto ns will not fl a sh Pl a tinum a n p a ll a dium a re

,
.

ex c ept ed

d
.

S ilv er be a ds a fter cupell a tion a n a t the moment of s o lidi ,

“ ”
fic a t io n a ls o spro ut
,
A ccording t o G a y Luss a c molten silv er
- .

dissolv es 22 ti m es its V o lume o o yg n a t the freezing p o int

f x e -
,
.

La t er resea r ch es l pro v e this p r a ctic a lly correct A t 1 020 C .

°
.

v olum es of o x yg en (a t 76 0 m m
d
m olten silver will h old
d
.

an
°
h
0 C) a n a t t e mel t ing p o int s o mewh a t more
- For .

a ny given temp er a ture the o x ygen diss o lved is p ro p o rti o n a l to the

squ a re ro o t of t h e o x ygen pressure In a ir a t 76 0 mm pressu r e

d
. .

the o x ygen h a s a p a rti al pressure of 1 50 mm a n the v olume .

o f o x ygen diss o lv ed by molt en silv er under a ss a y c o nditi o ns is

volumes a t the freezing point of silver T h e oxygen is -

.

dissolved eith er a s m o n a t o mic oxygen or a s silver oxide (A g 2 0 ) ,

in dilute s olution It is prob a ble th a t this sil ver oxid e no t

.
,

being solubl e in solid silver is dissoci a t ed with e x plosive vi olenc e ,

with t h e lib er a tion o f o x ygen wh en t h e silver solidifies , .

This o x ygen suddenly e x p ell ed wh en the be a d s olidifies c a us es

, ,

a c a u liflo w er like gro wth on the be a d S m a ll p a rticles of silv er

d
- .

m a y ev en be proj ected from it a n c a use a seri o us l o ss Wh en .

go ld is present in the S ilver be a d t o the e x tent of 3 3 per cent or .

m o re spro uting d o es no t t a ke pl a ce S ilver bea ds cont a i ning

,
.

sm a ll qu a ntiti es o f Pb Cu Z n Bi etc will not s p ro ut so th a t , , , ,

.
, ,

if a butto n d o es spro ut it is a sign of purity .

Buttons b el o w 5 mgs in weight do no t sprout re a dily ; l a rge

d d
.

butt ons h o wever ,

o S pro uting c a n be prevente
,
.by sl o w
c o oling in the mu ffl e o r by h a ving re a dy a h o t cupel which ca n
d
,

be set inverted over t h e one h olding the be a d a n withdra wing

, , ,

b o th fro m the m u ffl e thus cooling the be a d slowly S pro uted ,

.

be a ds a r e t o be rej ect ed a s a n a ss a y
d
.

Wh en cup elling fo r silver a l o ne o r fo r silver a n gold it is

d
, ,

necess a ry t o w a t ch the end o f t h e cupell a ti o n c a refully a n to ,

pro m ptly r em o ve t h e cup el a b o ut 3 0 sec o nds t o 1 minute a fter

t h e b ea d h a s b ec o m e dull A h ea vy l o ss of silver c o mm enc es if .

the silver buttons a r e kept beyo nd th a t ti m e in the furn a ce If .

silver is no t t o be determined b ut go ld o nl y the buttons m a y , ,

1
D o nna n a n d Sha w . J our . S oc Ch em I n
. . dXXIX
.
, , 987 . S iever ts un dH a g enac ker ,

Z eit P h ys Ch em . .
. XVIII
L , 1 15 .
84 A MA N UAL OF F I RE A SS AYIN G

be left i n for 5 to 10 minutes wi thout lo ss of gold G old be a d s .

will ret a in minute a mounts of le a d which c a nno t be removed by

p ermitting the be a d to st a y in the mu ffle .

It is to be noted however th a t sil ver le a d all oys cont a ining

d
, ,

between 80 a n 90 p er ce nt of silver a lso S how the p henomenon of

.

spro uting o r developing a c a uliflow er like growth o n solidific a tion l

-
.

The be a d when cold is t a ken from the cupel with a p a ir of

d
, ,

pliers a n cle a ned of bone a sh by fl a ttening somewh a t with a

,
-

h a mmer It should be ex a mi ned with a gl a ss to m a ke sure th a t

.

no bone ash a dheres t o it

- .

The be a d should be either white o r yellow depending on the

d
,

a mount of gold present r o und a n not fla t (the l a tter indic a ting

d
,

the presence of fo reign met a ls) a n sh o uld possess a cryst a lline ,

surf a ce where it a dhered to the bone a sh It sh o uld be firmly

- .

a tt a ched to the bone a sh of the cupel

- If it is not this f a ct .
,

indic a tes th a t le a d is still present It should a lso h a ve no rootlets .

dd
exte nding i nto the cupel T h e cupel a fter cupell a tion should
d d
.
, ,

be smooth a n firm no t fissu r e a n cr a cked a n of a light

, ,

yell ow c olor when cold Other colors indic a te the p resence of

.

foreign met a ls .

The freezi ng point cu r ve of le a d silver (Fig 48) will give

- - .

d
some ide a of the proper temper a ture of cupell a tion A le a d .

butto n is t o be considered as a n a lloy of le a d a n silver (or gold)

which in t he process of cupell a tion undergoes the ch a nge from
pr a ctic a lly pure le a d to th a t of pure silver (or go ld) .

A 20 g r a m button cont a ining 200 mgs of silver cont a ins

d
-
.

1 per cent of A g A n al loy of le a d a n silver cont aining 4 per

d
. .

”
cent of A g is of eutectic comp o siti o n a n melts a t 3 03 C
.
°
.
,

the melting point of pure le a d being 3 27 C Most a ss a y buttons

d
- °
.

will cont a i n very much less th a n 1 per cent of silver a n will .

melt pr a ctic a lly a t the melting point of le a d Le a ving out of - .

“ ”

d
considera tion for the moment th a t le a d uncovers a t 8 50 C °
.

in a n oxidizing a tmosphere a n the proper temper a ture required ,

t o c a use a re a dy a bsorption of Pb O by the cupel it i s evident

d
,

th a t for a le a d button weighing 20 gr a ms a n c o nt a ining 20 mg s .

of silver per the tem per a ture required to keep the

button molten r a nges from 3 27 C to 3 03 C until the button °
.
°
.
,

h a s decre a sed Q1} in weight by the loss of Pb pr a ctic a lly the ,

entire time of cupell a tion .

When the button h a s re a ched 1 1, of its ori g in a l weight th e

1
,

1 . d
K Frie ich M t l l u g i III 3 98
r , ea r e, , .
86 A M A N UAL OF FI RE ASSAY IN G

tha t temper a ture of a b o ut 8 50 C is best fo r the m a in p a rt of °

a .

t h e cup ell a tion It is evid en t h o wever th a t in o rder t o finish

.
, ,

d
t h e cupell a t i o n the he a t must b e r a ised t o w a rd the end o ther
, ,

wise the a ll o y o f le a d a n s ilver a s it increa ses in silver percent ,

a g e will tend t o freeze i s

,
to s olidify It is a lso to b e noted
,
. .
,
.
,

h o wever th a t this tendency with m o st l ea d butto ns of ordin a ry

, ,

silver contents is not re a ched until very ne a r the end o f the

d
,

cupell a tion It is a n ol s a ying a mongst a ss a yers th a t a c ool “

d
.

”
drive a n a h o t blick a r e essenti a l to a good cup ell a ti o n In the .

cup ell a tion fo r S ilver it wo uld seem a t fi r st sight th a t a fin a l

temper a ture of 96 2 C is necess a ry in o rder t o prevent freezing
d
°
.

an to o bt a in a silver b ea d free fro m l ea d H owever the phe .

,
“ ”
no meno n o f the surfusion o f the silver i e silver in a molten ,
. .
,

s t a te bel o w its tru e m elting p o int due p r ob a bly to its form a ti o n

-
,

fro m its le a d a ll o y by t h e o x id a tion o f t h e le a d a ppe a rs t o indic a te ,

th a t this temp er a ture is no t necess a ry It is true neverth eless .

, ,

th a t the finishing temper a t ure depending som ewh a t upon t h e ,

a mount o f S ilver pres ent m a y no t f a ll much b el o w 9 1 0 C

°
.
,

It is pl a in th a t buttons m a y be cupell ed a t temp er a tures much

a bove those st a ted but the l o ss of silver a n gold both by a b d
d
, ,

sorpti o n a n vol a tiliz a tion is ve r y much incre a sed with the ,

higher temper a tures .

The re a soning o utlined fo r silver a ppli es a lso t o gold except ,

th a t o wing to the s o mewh a t higher m elt ing p bint of go ld

,
-

( 1 06 3 °
the fi ni shing temper a tu r e sh o uld b e a little higher .

It is of interest a t this point t o m o re fully discuss t h e question '

of t emp er a ture of cup ell a ti o n This term h a s b een used in a

d
.

v a gu e m a nner by writers on the su bj ect a n h a s been used t o

signify general ly the tempera ture of the a ir o f the mu ffle eith er ,

a t the side o r j ust a bove the cupel o r th a t o f the int eri o r of t h e ,

cupel Du e to the h ea t o f c o mbustion o f t h e l ea d n either o f

.

these tempera tures is t h e true temper a ture o f cup ell a ti o n The .

a ctu a l temper a ture o f cupell a ti o n h a s o nl y recently b een d et er

mined 1
ue
,
d
pro b a bly t o t h e f a ct th a t this d et ermin a ti on
inv o lves e x periment a l di fficulti es since t h e p r o tective tube o f ,

the thermo coupl e in a lm o st a ny f o rm is r a pidly d estro yed by

t h e c o rrosive a cti o n o f the lith a rge A s a lrea dy st a t ed th r ee .

d
temp er a tures m a y be c o nsidered du r ing cupell a ti o n ( 1) .

The temper a ture o f the cupelling le a ; (2) th e t emp er a ture of

H Fulto n dO d dI G d West
Ch em a n dM IV
dm
31
d mp
1 C . . an . A An erso n an . E . oo ner , . . et ,

w hich consul t for meth o s of te er a t ur e eter ina tio ns o f cu p ell a tio n .

 C U P ELLA T I O N 87

the mu ffle a s determined by th a t o f a bl a nk cupel a dj oini ng the

d
,

on e c ont a i ni ng t h e le a d ; a n ( )
3 the tem p er a ture o f the a ir

immedi a tely su rrounding the cupel This is inv a ri a bly lower .

th a n the fir st t w o temper a tures which a ccount s for t h e low

,

IN G ra ms Lea d

o z 4
M i nutes

FI G . 50 — T E M FE R A T U a E -CUR V E
. SHOW I N G D FFE RI E N CE B ET W E E N A IR IN MU FF LE
AND CU P LL N G LE
E I A D.

temper a ture figures th a t h a ve been a ssi gned to the cupell a ti o n

proc ess It is to be no ted th a t there is a n a ir dr a ft through the
.

mu ffl e during cupell a tion cold a ir const a ntly entering a t the

,

m o uth of the mu ffle so th a t the a ir in the mu ffle does not a tt ain

,

the tem p era ture of the mu ffle w a lls The a ctu a l a ir tem p er a ture
.
88 A M A N UAL OF F I RE ASSAYIN G

is a lso pro b a bly somewh a t lower th a n the th ermo couple j uncti o n

shows since t his a bs o rbs he a t ra di a ted fro m the muffle w a lls
d
, ,

more r a pi l y th a n the a ir Fig 50 shows the t w o tempera ture

d
. .

curves one the a ctu a l tempera ture of the c upelling le a d a n t h e

d
, ,

other th a t of the a ir in the mu ffle close by a n a t a level with

d
,

t he top o f the cupel The genera l fo rm of the curve is u e to

d
.

fluctu a tions of tempera ture in the mu ffle c a used by firing a n

d
,

a ttempts t o re g ul a te the temper a ture by dr a ft a n otherwise ,

.

It will be noted th a t the tempera ture of the cupel rises r a pidly

d
a fter oxid a tion h a s c o mmenc ed a tt a ining a m a ximum o f 94 0 C
°
.
,

then f a lling a s the mu ffle co oled T h e interesting d a t a is the

d
an .

di ff erence betwe en the tempera tures of the a ir in the mu ffle a n

the cupel which is gre a test during the perio d of a ctive oxid a ti o n
,
.

“
The m a ximum diff erence is 1 4 5 C The le a d froze or w a s ” °
.

covered over with a co a ting of Pb O preventing further cu p ella ,

tion a t 8 02 C the a ir in t h e m uffle being then a t 6 7 5 C The

°
,
°
.

a ctu a l minimum t emp er a ture o f cup ell a tion in this c a se w a s

th erefo re 8 02 C 1 2 7 high er th a n the a ir tempera ture

°
.
,
1 °
.

E x p er i ment — T o d etermine the t emper a ture o f the o pening

o r unc o vering o f the butt o n ; i e the b eginning of cupell a tion

d
. .
, ,

a n the
“ ”
freezing o f the button ; t e where cupell a tion is sto pped ,
. .

by the form a ti o n o f Pb O which is no t a bsorb ed .

In this e x periment 1 3 4 gr a ms o f le a d were used The p res ,

.

ence o f gold or silver h a s no influence on the se critic a l temper a

d
tures a s the m elting point of the a lloys is usu a lly f a r b elow the
,
-

“uncovering ” t emp er a tures a n the precious met a ls fo r m no

o x ides which wo uld c o mplic a te m a tters The influence of such .

met a ls a s c o pper will be referred to further on The set w a s ru n .

with a bl a nk a t the s a me tempera ture a s the cupel before the

,

d
le a d w a s a dded Fig 5 1 giv es t h e curves pl o tted a s b efore The
. . .

resul ts show th a t the butto n begins t o unc o ver a t 8 00 C a n

d d
°
.

8 04 C a n begins to freeze
°
.
“ a t 8 04 an 788 C These a re ° °
.

the a ctu a l cup el tempe r a tures A repetition of the experiment

d
.

“ ”
in the s a me cupel shows uncovering a t 83 2 C 8 29 C a n ° °

d
.
,
.
,

Other results show the begin

d
8 3 4 C a n a fre ezing a t 8 5 0 C
°
.
°
.

“ ”
ning of uncovering a t 79 7 C a n completely open a t 8 05 C °
.
°
.

A nother shows a n op ening to occur a t 8 1 1 C A n o ther shows °

.

d dfi y pr o v e d p d xd
d yd d
ifler ence in te m er a tur e t o b e ue t o th e o i a ti on
d d
nitel
'
1I n or er to e th e
p
dp
o f th e lea b l i h l
xd
, a se t w a s r u n in w hi c h th e l ea in t h e c u el w a s co v er e y a c a s u te o n,

p y p m y
d
r a c tic a ll r ev enti ng o i a tio n I n t hi s inst a nc e th e m u s a n c u el w er e a t nea rl
.

p p
th e sa me te m er a t ure for th e s ac e o f a n h o ur , rst one b eing a lit t le h ig h er a n th en th e fi
o th er .
90 A M A N UAL OF FI R E ASSAYIN G

unc o v ering a t 8 26 C ; a nothe r e x periment a t 809 C

d
° °
an .
, .

In gener a l the o peni ng t emper a tures a n freezing temp era tures

,

a r e ne a r ea c h o ther a s is t o b e exp ected in so f a r a s t h e t w o a r e

, ,

in the a bsence of a ny silic a pr a ctic a lly the result o f t h e s a me ,

process The freezing t emp er a ture howev er ma y be som ewh a t

.
, ,

higher or l o wer fo r a number of re a sons d eveloped b elow These .

critic a l tempera tures a re of imp o rt a nce in so f a r a s they m a rk the

minimum p o ssible temp er a ture o f the beginning of cupell a tion .

F ro m the curves it will be noted th a t a s soo n a s the button

uncovers there is a sh a rp rise in the t empera ture of the l ea d
d
,

wh ether the mu ffle t emper a ture rises or no t u e t o t h e o xid a ti o n

d
,

o f the l ea d In the curv es where the mu ffle bl a nk a n the cup el

.

were a t t h e s a me temper a ture before the d r o pping in of the le a d ,

the oxid a ti o n ra ises the cupel temp er a ture from 20 to 1 50 C ° °

.

a b o ve th a t of the mu ffl e d epend ent upon the r a te o f o x id a ti o n ,

i e the a ir supply
. .
,
S ince it h a s be en w ell est a blish ed th a t the
.

chief c a use d et ermining t h e l o ss o f precious m et a l by a bso r pti o n

an d
vol a tiliz a ti o n is the te m p er a tu r e it is a t once a pp a rent th a t ,

f o r c a reful w o rk t h e a ir supply o f the mu ffle is j ust a s i m p o rt a nt

a s a r eg ul a t io n o f the temper a tu r e of the mu ffle itself In Fig . .

5 1 the cup el t emp er a ture d o es not rise gre a tly a bove the mu ffl e
temp er a ture This is due t o t h e f a ct th a t j ust a s s oon a s the
d
.
,

le a d h a op ened the furn a ce w a s a g a in c o ol ed in o rder t o g et a

,
“
d et ermin a ti o n o f the te m pe r a tu r e of t h e freezing thus pre ”
,

venting the a tt a inment o i m a x imum o xid a ti o n

d
.

“
Wh a t d et ermines t h e unc o vering a n ” “
freezing of th e
buttons ? It wo uld a ppe a r a t first sight th a t the critic a l tem
f uncovering ” “ fr ezing ”
is the m lting p int f d
d
p e r a t u r e o a n e e o o -

lith a rge in so f a r a s the m elting o f t h e c o ver o f o x ide a n its

,

a bs o rpti o n by the cup el would n a tur al l y m a rk the

“ o pening
”

d
.

R ecent a n a ccur a te determin a tions o f the m elting point o f pure

d
-

lith a rge give 906 C a n 884 C with the l a tt er prob a bly t h e

1
,
2 °
.
°
.
,

d
figure t o be preferred In these resea rch es it is noted th a t b e .

—
fo re the melting point is r ea ch ed th ere is a decid ed so ft a n
p a sty st a ge which is a scrib ed t o t h e m a r ked v ol a tiliz a ti o n o f Pb O
,

f r o m the s olid st a te This v ol a tiliz a ti o n b egins j ust below

d d
.

8 00 C a n is a functi o n oi t h e a rea ex p o sed a n the t emp er a

8
°
. .

t ure A s in t h e c a se und er c o nside r a ti o n the film o f Pb O on

.
,

1 O . D oel tz an d
M o s to w i tsc h , M eta l l u r g i e , IV , 2 90 .

M o sto w i tsc h M IV
d
1
, eta l l u r ai e, , 4 68 .

3
O D oelt z
. an C . A . G r a uma nn, M eta ll u r ai e, III , 408
.
 CU P ELLA TI O N 1

th e butto n g ives prob a bly the gre a test a rea in rel a ti o n to v olume
p o ssible this vol a tiliz a ti o n is a n imp o rt a nt f a ct o r in the un co ver
,

ing of the butto n in the c a se of the a bsence of silic a o r b o r a x

d
, ,
“
an the pr a ctic al ce a sing of this v ol a tiliz a ti o n m a rks t h e fr eez
”
ing of the butto n It will b e noted th a t a ll the temp er a ture
d
.

” ”
determin a tions of the opening a n free zing a r e well be
lo w the melting point of lith a rge - It is here self evid ent th a t .
-

when a butt o n is put into a cupel wh o se t emp er a ture is 900 C

d
°
.

”
an a b o ve th a t the t emp er a ture a t which
,
openi ng is o bserved
h a s no speci a l sig ni fic a nce .

Le a d butt o ns from crucible a ss a ys p r a ctic a lly a lw a ys h a ve

a dhering to them sm al l a mounts of silicio us sl a g a n the b o ne ,
d
a sh a t times cont a ins minute qu a ntities o f S iO, When the le a d
d
.

butt o n melts in the cupel this sl a g a n fine loose bone a sh g o t o , ,

-

the surf a ce int o the lith a rge film A c c o rding t o recent rese a rch
d
.

o n the l ea d silic a tes

1
the silic a tes 5Pb O S iO, a n
d
-
.
,

4 Pb O S iO2 a re thi nl y fluid a t 7 94 C 796 C a n 7 26 C r esp ec

.
°
.
,
°
.
°
.

t iv ely The percent a ge c o mp o sition of these silic a tes is a s

.

f oll o ws
'

S ilic a te Lith a rge S il ic a

6 Pb O S iO, .

5 Pb O S iO2 .

4 Pb O S iO, .
'

It is evi dent th a t when t he v ery sm a ll a mount o f lith a rge

which forms the fil m is considered th a t minute qu a ntities o f sil ,
”
ic a o nl y a r e necess a ry to m a teri a ll y l o wer the o pening t em
p e r a t u r e o f the butt o n F r o m thes e f a cts it f o ll o
. ws th a t the
” “ ”
opening o r uncovering temper a ture is no t a fixed temp er
a ture but will depend upon the following f a ctors
,

1 The presenc e of silic a in a conditi o n to combine with

.

le a d (very prob a bly a lso of b o r a x ) Where this silic a c o mes .

from h as a lre a dy been menti o ned .

2 The v a po riz a ti o n o f s olid lit h a rge A s the r a te of v a p o r

d
. .

iz a tio n depends upon t h e temper a ture a n the rel a ti o n of ,

a rea e x pos ed t o v o lume present a butt o n with a thick cov ering ,

will no t Op en a t a s low a t emp er a ture a s one with a thin c o v er

ing This ca n be de m o nstra ted by pl a cing a butt o n in the cup el
d
.

a t a temper a ture b el o w 7 00 C a n pe r mitting it t o form a h ea vy °

. .

“
film o f Pb O then r a ising t h e temper a ture to the usu a l unco v
,

1 WI Mosto w itsch M eta ll ur oi e I V , 64 7

'

. .
, ,
92 A MA N UAL OF FI RE ASSAYIN G

ering point a n pl a cing a noth er butt o n int o a second he a ted

,
d
cupel The l a st butto n will uncove r first a s its thinner c o ver o f
.
,

lith a rge will v a po rize in less time .

3 The presence of foreign met al s in the le a d such a s cop

.
,
“ ”
per iron etc will r a ise the uncovering t emper a ture This
d
.
, , , .

is a frequentl y o bserved f a ct a n the re a so ns fo r it a r e pr a ctic a lly ,

obvious If the tempera ture o f the cupel a t the mom ent of u n

.

c o vering c o ul d rem a in fix ed the incre a se in the o xid a tion of ,

the le a d would very so on b a l a nce the v a p o riz a tion a t th a t tem

p e r a t u r e a n the button would a d
g a in fr ee z e but it h a s a lre a dy ,

be en noted th a t a very sh a rp rise in temper a ture a t once occurs

a utom a tic a lly ; i e independent o f the mu ffle due to the r a pid
. .
, ,

o x id a tio n o f the le a d ; this e ff ects a m a rked incre a se in v a poriz a

tio n keeping the button o pen a n so o n in m o st inst a nces the d
d
,

tempera ture of the butto n itself p a sses t o a n beyo nd the melt

ing point of lith a rge an cupell a ti o n proceeds r a pidly d .

Cup ell a ti o n h o wever c a n seemingly be c a rri ed on b el o w the

d
, ,

melting p oint o f lith a rge a s Figs 5 1 a n 52 will sh o w The

-
, . .

p a rticles of lith a rge fo rmed on the surf a ce of the butto n th o ugh

d d
,

s olid a r e p a sty a n c a p a ble of b eing a sb o rb e by the cupel

, ,

or t h e surf a ce o f the cupelling l ea d being the a rea o f the m o st

a ctive o xid a tion is a t or a b o ve the temp er a ture o f melting

lith rge which the th ermo j uncti o n a t the bottom of the l ea d

a ,
-

does not indic a te 1

.

In o ne experiment c o nt a ining c o nsider a bl e silver it w a s

d
, ,

n oted th a t very ne a r the en of the cupell a tion when the a m o unt

of silver w a s l a rge a n th a t of le a d sm a ll the butto n w a s cupel d ,

ling a t a n indic a ted cup el tempera ture o f 7 50 C the button then

d
°
,
.

solidified a n proved to be a l ea d silve r a ll o y The t emper a ture -

.

o f 75 0 evid ently did not represent the surf a ce temp er a ture of

°

the button a s w a s indic a ted by the brigh tness o f t h e Pb O specks

formed ; i e the a mount of he a t liber a ted by the sm a ll a m o unt
. .
,

of le a d o x idized w a s insu fli cient to m a ke a ny m a t eri a l impressi o n

on the thermo j unctio n
- .

T he
“ F reezi ng
”
of the Bu tton — Wh en the temper a ture of
the mu ffle f a lls so th a t t h e he a t of oxid a tion of le a d is no lo nger

xp d point p p d
d
ment m b O l i
d d
1 In an e eri , 70
to g r sh e
a s o f lig h t
u re P w on
er e this
ac e n a

p h ea te t o 8 1 5 C for t h e ti m e o f 2 0 mi nu tes T h e li th a r g e sh ow e v a or i a tio n , p z

d dp
°
c u el a n . .

p
er i m ent t h e tem er a t ur e w as xp p
d d
d
b u t no ne w as a bs or be b y th e c u el In a u lica te e

d
.

p
d
m w hile th e li th a r g e i no t m el t , a ll o f i t
d
- oint a n
h l i
pd
r a ise to 883 C j ust b
°
el o w t e e
. t ng ,

y p
I n th e rst c a se th e m a ss o f li th a r g e w as sinter e fi
d
w a s r a i l a bso r b e b y t h e c u el .
.

Ab p ti
sor on th us pr oba bly occ urs in th e p a sty ”
sta g e mentione .
94 A M A N UAL OF FI R E ASSAYIN G

gold or silver in a fused st a te will p a ss bel o w its solidifying

point without a ctu a lly solidifying but the slightest t o uch with a
d
,

m et a llic p oint will c a use the m et a l t o so lidify a n the consequent

rel ea se o f its l a tent h ea t o f fusi o n is su fli cient to r a ise the gl o b ul e
t o the melting p o int a g a in a s is indic a ted by the brilli a nt gl o w
-
,
”
which the butt o n emits R ose a ls o qu o t es the s a me a uth o r
d
1

d
.
,

an it is evident th a t the gold a n silver globules menti o ned a r e

d er ived fro m cup ell a tio n .

S ix s ets o f ex periments w er e c a rried o n in this c o nn ecti o n

d
,

some of which a r e pl o tted in Figs 52 53 a n 54 It is evid ent

d
. .
, ,

fro m th ese Figs th a t su r fusi o n unquesti o n a bly o ccu r s a n in a

.
,

most m a rked m a nner the gr ea test d egree o f surfusi o n not ed ,

“ ”
b eing 7 7 C A ll of the buttons spro uted i a sh o w ed c a uli
°
.
,
. .
,

fl o wer like growths of silver o n final solidific a tio n This sp r o ut

-
.

ing h a s a lw a ys b een considered a S ign of purity of the silv er 11

,

p a rticul a r ly p o inting to the a bsence of l ea d .

In o rder to t est this point som e of the silver butto ns fro m t h e ,

d
expe r im ents we r e very c a r efully ex a min ed f o r l ea d in qu a ntities o f

a gr a m a n sh o wed but tr a ces of it qu a ntiti es no t d etermin a ble

, ,
.

S o m e sh o wed minute qu a ntities of c o pper In e ff ect they were a ll .

fine silver The surfusi o n is th er efo r e ver y rea l In the

. .

a uth o riti es cited on surfusi o n the st a tem ent is m a de th a t o n ,

“ ”
s olidific a ti o n fro m surfusi o n the fl a sh o f the butto n o ccu r s , ,

sh o wing t h e r a ising of the t emp er a ture t o the m elting-p o int of

“
the silver H M H o we st a tes : Once freezing sets in (in t h e
d
3
. . .

m et a l o r a ll o y) t h e h ea t whi c h it evolves r a ises t h e

d
su r fu se

t emp er a ture t o w a rd a n m o re o ft en quite t o t h e tru e freezi ng

, ,
”
p o int wh ere it rem a ins du r ing t h e rem a ind er o f the freezing
,
.

In e x p erim ents c a r ried o n with t h e foll o wing qu a ntities of silv er

d
,

10 14 18 an 3 0 g r a ms t h e
“ ”
fl a sh w a s no t obs erv a bl e
, , , , ,

n either by the eye no r by a ny a ctu a l rising d efl ecti o n o f t h e

d
.

g a lv a no meter p ointer a lth o ugh a rep ea ted a n c a r eful s ea rch ,

w a s m a de fo r this In o r d er t o d etermine whether t h e size o f the

d
.

“ ”
butto n h a a ny influ en ce o n the fl a sh ing v a r i o us a m o unts o f
d
,

silv er b eginning wi t h 3 50 m g s a n v a rying by 50 mgs up to 8 50

, . .

mgs w ere cup elled so a s t o finish with surfusi o n It w a s fo und

d
. .
,

th a t t h e b ea ds up t o a n in cluding 6 50 mgs fl a shed m a rkedly

d
.
,

th a t o f 700 mgs f a in tly o nly a n thos e a b o ve sh o wed no fl a sh

.
,
.

M t ll g y f G ld 4 th E d p 5 98
R M t ll g f G ldp 4 77 C llin M t ll g y f S il 1 900 p 2 S h n b l
1 e a ur o o , .
, . .

d dd
ose , e a ur yo o , . . o s, e a ur o ver , , . . c a e ,

M e t a ll-Huet tenku n p
d
e, 1 90 1 , . 6 05 , 2 n E .

3
I r o n, S teel an O th er A lloy s , 1 9 03 , p . 20 .
 CU P ELLATI O N 95

If the di ff erenc es in t emp er a ture b etween the cupelling a lloy

an d the mu ffle bl a nk a t a ny time inter v a l be pl o tted a s o rdin a tes
f r o m a b a s a l line it is rea dily sh o wn by the di ff erent curves th a t
d
, ,

t h e g r e a test ifler ence o c c urs a t t h e cl o se o f the cup ell a ti o n ; in

so me inst a nces j ust a s the l a st of the l ea d o x idiz es (pl a y o f
,

c ol o rs) The di ff erences no t ed sh o w the m a rked ev oluti o n o f

d
.

“ ”
h ea t a t th e finishing o f the cupell a ti o n a n a r e due t o t h e ,

rele a se of the l a tent h ea t of fusi o n In the c a se of the l a r ge .

Ag . 14 G ra ms
Pb . : 65

D i ffer e nc e Cur ve

B a sa l L i ne

0 2 4 6 8 10 12 14 1 6 18 20 22 21 20 28 30 32 3 4 36 38 10 42 44 40 48 50 52 64 66 58 00 62 64 00 08 70
M i nut es

FI G . 52 .
—CUR V E SHO W G T M P R T UR E D UR G CU P
IN E E A IN E LLA TI O N OF Pb = A g .

butt o ns h o wev er this d o es no t seem t o be su ffi cient t o c a use a n

, ,

a ctu a l r is e o f t emper a ture in t h e cup el wh en t h e mu ffle temp er a ,

tu r e is a ctively sinking a s w a s t h e c a se in e x periments S h o wn

d
,

by Figs 52 53 a n 54 A s a l r e a dy st a t ed howev er no fl a sh
.
“ ”
,
.
, ,

w a s o bs erv a ble t o t h e eye in t h e l a r ger silver butt o ns no r did t h e ,

g a lv a nom eter indic a te it a s su r ely might be expect ed T h e

,
.

”
la g
d
or time inter v a l b etween t h e o ccurrenc e o f a t emp er a ture
an its rec o rding by t h e g a lv a no m eter is not gre a t Wh en a n ,

i r o n pro t ective tub e is empl o yed This is sh o wn very p l a inl y by

.
96 A MA N UAL OF F I RE AS S AYIN G

Note
d
l d
Const a nt i fference bet we en
Cupe a n M u m
°
s Bla nk B ” O -
18 G ra ms, A 3 .
85 u Pb .

D il erence Curve
Ba sa l Lin
e

0 2 4 6 8 10 12 1 4 Isw m u asaoazu asas “42 4440 4850 52“50 58 0062 04 00 08 701 2 24 7618 w82843 83 90929!
M inutes

FI G . 53 —CU R V E
. SHO WI N G T E M PE R T URE D U RI N G
A CU PE LLA TI O N or Pb = A g .

l d
d l
dd
S h o rt y before a it io n o f A l oy,
Te mpe r a t u res o i Cupe l an M e i a
l
B a nk w ere i ent ica d l
10 G ra ms. Ag
l
.

Basal Line
M inutes

FIG .
—
54 CUR V E
. SHOWIN G TE MPER A T UR E DUR I NG CUFE LLA T I ON o r Pb = A g .
98 A MA N UAL OF FI RE ASSAYI N G

Where very a ccur a te cupell a ti o n work is required such a s in

d
,

bulli o n a ss a ying a n wh ere the a m o unt o f work j us t ifies it a

d
,

furn a c e designed fo r cl o se temper a ture a n ai r c o ntrol is pr a ctic a lly

d d
essenti a l In view of the recent improvement in el ectric a lly
.

d
he a ted furn a ces in which t empera tures c a n be r a p i l y a n a o
,

c u r a tely contro lled a n the mu ffle h ea ted unifo rml y pr a ctic all y
, ,

elimina ting the th erm al gra dient a furn a ce o f this type would ,

seem b est a d a pted fo r the wo rk .

I NFLUE NC E OF BASE M E TAL I MPUR ITIES — Wll en the le a d .

buttons a r e c o nt a min a ted with b a se met al s such as c o pp er , ,

the te mper a ture o f cupell a ti o n must be higher in order t o p r e

vent fre ezing The re a s o n fo r this is re a dily a pp a rent when
.

the freezing p o int curve (S ee F ig 4 9) of the le a d c o pp er series

-
.
-

o f a lloys is inspected T h e f r eezing p o int of a n a ll o y c o nt a in

d
.
-

ing 1 0 per cent Cu a n 90 per Cent Pb is 900 C

. .
°
.

~
Whil e the o rigin a l copper percent a ge in the le a d butto n m a y
be quite sm a ll t h e c o pper does no t o xidiz e a s re a dily a s t h e l ea d
d
, ,

an tends t o con centra te in the button r a pidly r a ising the ,

melting p oint o f the a ll o y

-
.

Fo r the rem o v al o f c o pp er in cupell a ti o n the r a tio of Pb t o

d
Cu sh oul d be a t le a st 200 t o 1 o r m o re E v en th en Cu will b e r e
d
.

t a ine by the silver a n gold in sm a ll a m o unts If it is less th a n .

this c o nsider a ble c o pper is very a pt t o be ret a ined with t h e

d
silver a n gold In o rder t o cup el a t a ll the r a t i o o f Pb t o Cu
.
,

must be a t l ea st 20 to 1 In gener a l butt o ns to be cup ell ed

d
.
,

sh o uld be free f r o m b a se m et al impuriti es If they a r e u na v oi .

a bly pres ent in the butt o n fro m the crucibl e a ss a y the b a se m et a l s ,

sh o uld b e remov ed by sco r ific a t ion b efo re cup ell a tion .

Impu r iti es in l ea d buttons a r e d etected by the beh a vi o r o f

the butto n Z n A s S b a n S tend t o m a ke t h e butt o n brittle d
d
.
, , ,

when h a mm ered ; iro n a n c o pp er etc tend to m a ke it h a rd ,

.
,
.

Pb O in the le a d butto n m a kes it brittle Ph O is o ften f o und in .

l ea d butto ns th a t h a ve b een p r oduced a t t o o lo w a tem per a tu r e

d
.

Where the gold a n silver contents of the l ea d button a p pro a c h

3 0 per cent o f its weight it is b r ittle
.
, .

Ho wever impurities in the l ea d butt o n will no t a lw a ys be

,

indic a t ed by brittl eness o r h a rdness ; without these ch a r a cteristics ,

impuriti es m a y still be pres ent in su ffici ent a m o unt t o c a use loss

d
.

A ll i m purities o no t c a use like a m o unts of l o ss in c up ell a tion .

The l o ss due to the presence o f impurities is chiefly in a bsorp tio n

, d
by the cupel a n co mp aratively sm a ll by vol a tiliz a tion .
 CU P ELLA TI O N

The a ccomp a nying t a bl e shows the influence of impuriti es 1

.

Twenty fiv e gr a m le a d butto ns were cup elled c o nt a ining 1 gra m

d
- -
,

o f the impurity specifie d 4 mgs of A g a n 1 mg of A u The ,

.
,
. .

temper a ture of cupell a ti o n w a s 1 000 C in order to prevent °

.
,

freezing a s a result of impurity .

The high l o sses a r e due in p a rt t o the high temper a ture em

pl o yed The t a ble re a lly giv es the rel a tive influence o f t h e im
.

puriti es Bismuth h a s been used in pl a ce o f le a d fo r cup ell a ti o n

. .

Whil e in the t a ble bismuth is st a ted t o b e the c a use of a very

he a vy a bsorpti o n this is not subst a nti a ted by o th er resea rches “ .
,

When it is present in t h e l ea d butt o n it tends t o conc ent r a te dur

ing t h e cupell a ti o n a n is rem o ved by o xid a ti o n tow a rd the l ast ,
d
o f t h e o per a tion S o me of it is ve r y a p t to b e ret a ined by t h e p r e
.

cio u s met al b ea d Cup ell a ti o n ma y be c a rried o n with bismuth

.
,

but t h e a bsorpti o n is much higher 3

The presence of Bi in the .

c old cu pel m a y be r ec o gnized by the f a ct th a t the pl a ce which

the silver butt o n o c cupies is bro wn a n surrounded by concentric d
rings of a yell o w a n bl a ckish green c o l o r Co pper colors the
- d .

cupel fro m a dirty green t o a bl a ck dependent o n the a mount ,

o f c o pper .

TA B LE X M L I NFL UE NCE OF IMPUR I T IE S

—

l
I m p u r it y Loss of G o ld Lo ss of S i l ver R em a r ks

N one .

T in .

Ar senic
Antim o ny
Z inc .

Ca d m i u m
I r on .

Ma nga nese

Va na di u m
COpp er
Bismu t h 4

T ha lli u m
Tellu r i um
S eleni u m

K R ose , in J o u r Ch em M d
d d
1 T M i n S ec f S A Ja n 1 9 05
d
. . . . et . an . . o . .
, .

3
K Sa n er , B er g a n H u ett en ma enni sch e Z ei tu na , 1 903 , p . 81 . S ee a lso M in In
. .
.

XII , 24 4 .

3
S mi th , in J o u r Ch em S oc . . .
, 1 8 94 , 863 .

D o ub t u l f .
1 00 A M A N UAL OF FI RE A S SAYIN G

Tin a rsenic zinc c a dmium iron a n m a ng a nese c a use scori a

, , , , ,
d
to form on the cupel due t o the form a tion of oxides which a re
,

not re a dily a bsorbed Iro n c a uses a d a rk c olora tion of the cupel

. .

A ntimony in consider a ble qu a ntity c a uses the cu p el to check

an dcr a ck The s a me m a y be s a id of copper
—
. .

This met al is oxidized with more di ffic ul ty th a n le a d

d
COpp er .
,

the Ou zO forming by a i of t h e a ction of Ph O; however Cu , O , ,

a g a in c o ming into cont a ct with m et a llic le a d is reduced to Cu

d
, ,

d
an in this w a y is p ersistent tow a rd the end of the cupell a tion ,

a lth o ugh a l a rge excess o f Pb o v er Cu is present a n fin a lly some

d
,

rem a ins with the A u a n A g The loss of silver during the cupel .

l a tion is due m a inly to a bsorption in l a rge p a rt a s o xi de This ,

.

oxid a ti o n o f the silver in the p r esenc e of much le a d is not to be

a scribed t o the a ction of a tmosph eric o xygen but r a ther to ,
“o x gen c a rriers O O
d
y such a s Pb C,
u , etc It is very pr o b a ble , ,
.

th a t Cu 2 0 a cts peculi a rly in this m a nne r a n t h e high a bsorpti on ,

d
notic ed when Cu is present is due t o this f a ct It is t o be no ted .

th a t losses in silver o ccur to w a rd the end of the cupell a ti o n a n ,

occur in gre a t p a rt j ust before finishing ; the sm a ll bl a ck green-

rings surrounding the pl a ce where the silver be a d rests loc a tes

, ,

most of the silver It is the concentr a tion of the copper silver

d
.
, ,

an gold th a t c a uses the high a bsorption Lodge shows the1

.

influenc e of sm all a mounts of copper on the cupell a tion of

silver a n gold d .

TA B L E X I V .
— COPPE R I N C UPE LLAT I ON OF S I L VE R AN D G OL D

Per centa ge Tem per a t u re Percent

Lea d Copper
o f c o pp er degr ees cen a g e of
gra ms gr a ms
in lea d t ig r a e lossd
’

“
1 N A ssa ing ,
o tes o n y1 43 at p . sea
.

p
T em er a ture o f a ir in m u c u m
1 02 A M A N UAL OF FI RE ASSAY IN G
TA B LE X V .
— TE LL U R I UM I N C UPE LLAT I ON OF G OL D AN D
S I L VE R

Loss by v o la t i li
Cont a i ning Loss by a bsorp tion za t iOn

p er c ent .
p er c ent .
p er c ent .
p er c ent .

24 7 6 5 04
2 3 64 4 81
1 8 42 3 75

C U P E LL E D . W I TH 1 2 GRA MS OF LE A D

N o te the simil a r eff ec t of s el enium .

A nti mony — The presenc e o f a ntimony c a us es in crea sed loss es

.

by a bso rpti o n a lthough its eff ect is no t a s pro no unced a s th a t

d
,

of copper o r tellurium D uring the cup ell a ti o n lith a rge a n .

a ntim o ny c o mbin e t o f o rm a nti m o ni a te o f l ea d which if present , ,

in consid era ble a m o unt m a y c a use t he fo r m a tion of sc o ri a o n ,

the c upel S m a ll a mounts of a ntim o ny t end to rem a in with the

d d
.

go ld a n silver a s with c o pp er a n t ellu r iu m

,
.

A s a guid e in c up ell a t i o n t h e f o ll o w ing sc a l e of c o lor t emp er ,

a tures is giv en
2
.

D egr ees Cent igra de

Low est r e vi sible in t h e da r k d 4 70
Da r k blo od r e o r bla c k r e d d
d d
53 2
d
- -

D a r k r e b loo d r e low r e 5 66
d
-
, ,

Da r k cherr y r e
d d
63 5
- .

Cher r y r e fu ll re 74 6
d
-
,

Light cher r y lig ht r e 84 3 ,

900
Light or a n e g 94 1
Y ello w 1 000
Light yello w 1 08 0
Whi te 1 205

CU PE LLATI ON I N C UP E L S OF DI FF E R E NT M AT E R IAL — The

cup el m a teri a l h a s a d ecid ed influenc e o n t h e p r o gr ess o f a cu p ella
ti o n Wh a t h a s p r ec eded refer s m o re p a rti c ul a rly t o bone a sh
.
-

d
d
1 S eleni um inste a o f tellu r iu m .

2
W
hi te a n Am M ch E ng XX I 6 28 H M H ow e in
d
T a y lor , in T r a ns . . S oc . . .
, , . . . .

E ng . an M in . J o ur . , LX IX , 75 .
 CU P ELLA TI O N 1 03

cupels In cupels wi th a m a g nesi a b a se the process a s reg a rds tem

d
.

p e r a t u r e di ff ers somewh a t u e to t h e di ff erent therm a l properties

,

of the t w o types of m a teri a l The fo ll o wing di ff erence in therm a l .

properties ma y be noted Bone a sh cup el me a n sp ecific he a t

d
1 - .
,

between 1 5 a n 1 00 C is Ma gnesi a cupel me a n specific

d
° °
.
,

b o ne a sh a n

d
he a t for s a me tempera tures is A - m a g nesi a
c upel of identic a l volumes weigh respectively 22 a n 29 gr a ms .

The he a t c o nductivity of m a gnesi a cupels is very much gre a t er

th a n th a t o bon a sh cupel s Wh en the t w o types of cupels a re
f e- .

he a ted t o 90 C in a ste a m b a th a t the end of 14 minutes the

d
°
.
,

m a gnesi a cupels a r e a t 90 C a n the bone-a sh cup els a t onl y °

.

60 C °
.D uring cupell a ti o n of le a d a t the end o f 6 minutes fro m
the a ddition o f the button the m a gnesi a cupel showed pra ctic a lly
the s a me tempera ture in the cupelling le a d a s in the bott o m of the
cu p el vi z 920 C W hil e the b o ne a sh cupel in the s a me mu ffle
d
° -
. .
, ,

showed a temper a ture o f 9 9 0 C f o r the cup elling le a d a n o nly °

.
, ,

93 2 C in t h e bottom
°
. The t o t a l he a t c a p a city of a m a gnesi a
.

cupel is more th a n 50 p er cent gre a ter th a n th a t of a b o ne a sh - .

cupel of the s a me volume so th a t on c o oling the two types o f ,

cu pel the m a gnesi a cupel ret a ins a higher temper a ture so mewh a t
longer th a n the bone a sh cupel in spite o f its gre a ter i ff usivity
- d
F ro m this d a t a the rea son of the beh a vior of ma gnesi a
d
o f he a t .

bone a sh cupels during cup ell a tion is a pp a rent It will be

d
an - .

n o ted : ( 1) Th a t in m a gnesi a cupels the le a d is less bright a n

hence a t a lower tempera ture th a n in b o ne a sh cupels a lth o ugh -
,

the mu ffle tempera ture is the s a me This is due t o the f a ct th a t .

the extr a h ea t gener a t ed by the combustion of the l ea d is dif

fused a s ra pidly a s gener a ted by the superior di ff usivity o f the
d
m a gnesi a cupel a n hence c a nn o t s erve to r a ise t h e temper a tu r e
of the le a d a s is the c a se in the bone-a sh cup el
,
H ence for .

the s a me m u ffle tempera ture the a ctu al cup ell a ti o n tempera

”

ture of the l ea d in the m a gnesi a cupels is 50 to 6 0 C l o wer

d
° °
.

th a n in the b o ne a sh cup els T o this f a ct is u e the l o wer

-
.

losses of precious met a l in m a gnesi a th a n in bone a sh cupels - .

F rom the discussi o n under cupell a ti o n temper a ture it will h a ve

been noted th t with bone a sh cup els if once the mu ffle h a s
a -
,

a tt a ined a temp er a ture su fficiently high to c a use the uncovering

o f the butt o n the rise in temp era ture of the le a d due t o its
,

dd
oxid a tion is su fficient t o c a rry t h e cup ell a tion t o a fi nish pr o
,

vi e the mu ffle temper a ture is not lowered a t the end of t h e

1 B nni t
a nd S t nl y
s er a T h m l P p e ti
a f Cup l
e . B ul 56 I M M
er a ro r es o e s. .
. . . .
1 04 A MA N UAL OF F I RE AS S AYIN G

per a tion Thi s is no t t h e c a se with m a gnesi a cupels for now

d
o .

o bvio u s re a sons an

d
it will b e necess a ry to r a is e the mu ffle tem
,

p e r a t u r e tow a rd t h e en of the oper a ti o n or wh a t a mounts to the

s a me thing push the cupel t o t h e hotter p a rt of the mu ffle
,
.

A ss a yers w h o a r e used to bone a sh cupels theref o re h a ve s o me -

, ,
“ ”
di fficulty a t first due t o f reezing of buttons when using
m a gnesi a cupels .

2 Ma gnesi a cupels ret a in a high er temper a ture l o nger th a n

.

bone a sh cupels when withdr a wn fro m the f urn a ce or m o ved t o

d
-

the cool p a rt of the mu ffle a n hence silver butt o ns sh o w a ,

lesser tend ency to spro ut due t o the sl o w cooling they undergo

,
.

The le a d in m a gn esi a cupels seems to Open somewh a t more

d
re a dily a n cupels slightly f a ster th a n in b o ne a Sh cupels - .

The a cc o mp a nying t a bles g ive d a t a of results obt a ined by b o ne

a sh a n d
m a gnesi a cupels on pure silver a n on a c o pper m a tte 1
d .

TA B LE X V I — C OMPA R IS ON OF B ONE A S H A ND
.
- MAG NE S I A
C UPE L S O N C P S I L VE R C UPE LL E D WI T H 1 0
. . G R AM S
SH E E T L E A D

Ma gnesia cu pels
(M or ga nit e)

The sheet le a d used cont a ined a little silver Cupell a tion in .

m o st c a ses w a s c a rried out with fe a thers It is t o b e noted th a t .

when lo w finishing tem p er a tures a r e empl oyed a s is a pt to b e ,

the c a se with m a gne si a cupels the be a d s m a y r et a in sm a ll ,

By 0 A A nd n nd
1
. . C H Ful t n S D S h l f Min
erso a .L b t y
. o , . . c oo o es, a or a or .
1 06 A M A N UAL OF F I RE ASSAYIN G

c upelled wi t h a bout 20 gra ms o f le a d The temper a tures were .

1

m ea sured by inserting a th er moc o uple i nt o a h ol e b o red bene a t h .

the b o wl of the cupel They hence represent a tem p er a ture which

d
.

“
is a mea n between th a t of the cupelling le a d a n a mu ffle bl a nk
c upel .

T A B L E X VI II — C UPE LLAT I ON L OS SE S WI TH DIFFE R E NT

.

TYPE S OF C UPE L S .

A ge
ver a U . S . P o r tla n d R . D Po r tla nd
. nh f cem ent
O e al
-
, Bone
tem p c em ent , cem ent , o ne-ha lf b one-a sh

d
.
, a sh , lo ss
eg . C . loss p er c ent . lo ss p er c ent . loss p er c ent .
p er c ent .

A n o ther
test t o a bso rpti o n d et ermine t h e
b n rel a tive e-a sh

d
of o

an cem ent cup els g a v e the following results : On 1 0 mgs

2
.

silver with 1 5 gra m s l ea d a t a n o r a nge h ea t (v er y high) cement

d
,

cupels sh o w ed per c ent a bso rpti o n a n b o ne a sh cupels

- .
,

per cent A t a light cherry he a t c ement cup els sh o wed

d
.
,

per cent a n b o ne a sh
-
p er c e
.nt a bs o rption It is t o . .

be no ted th a t t h e perc ent a ge a bsorpti o n o ther f a ct o r s being equ a l

is depend ent on the a m o unt of prec io us met al cup elled (see
p . In using cem ent cupels the b ea ds must be c a refully ,

cle a ned o th erwise wh en p a rting in nitric a cid insoluble S ilic a

is a pt t o rem a in which will be w eigh ed a s gold The be a d on .

c ement cupels is likely to b e m o re fla t th a n o n b o ne a sh cup els

- .

1 Holt an dCh r iste nsen, E ng . an d

M i n J our
. .
, X C 560 , . E xp er i ments w ith Po r t la n d
Ce m ent Cu pels "

d
.

2
J . W . Merr it t , Cement vs
. B o ne-ash Cu pels , M in . a n S ci P r ess
. .
, C, 64 9 .
 PA R T I N G

P a rting is the sep a r a tion o f gold fro m silver by me a ns of

a cid In a ssa ying nitric a cid is a lmost ex clusively used a lth o ugh
.
, ,

sulphuric a cid m a y be empl o yed In o rder t o sep a r a te silver .

fro m gold by me arns of a cid it is essenti a l th a t there be present ,

a t le a st twi ce a s much silv er a s gold Wh en less silver is present .

,

it is impossible to s ep a r a te a ll o f the silver fro m gold by me a ns

o f a cid (see a ss a y of gold bulli o n in Ch a pter X II ) When the ,
.

a bove st a ted a m o unt is pr esent it requires a cid o f not less th a n

-
,

specific gr a vity boiling for a t l ea st 20 o r 3 O minutes t o

d
, , ,

s ep a r a te t h e silv er fro m go ld The r a tio o f 2 a n t o 1 is .

used pr a ctic a lly o nly in t h e bulli o n a ss a y .

In p a rting b ea ds fro m or e a ss a ys it is c o nsidered necessa ry ,

t o h a ve a t l ea st five times a s much silver a s gold pr es ent T he .

a ddition of silv er t o go ld o r t o the gold silv er a ll o y in order t o -

“ ”
prep a r e fo r p a rting is termed inqu a r t a ti o n from the fa ct th a t ,

a t le a st 3 p a rts o f silver t o 1 p a rt of g old w ere formerly con

dd
si er e necess a ry The nitric a cid used for p a rting must be free
d
.

fro m hydro chloric a cid a n chl o rine in ord er not to h a ve a solv ent
a ction o nth e go ld N itric a cid should be e x a m ined fo r chl o r ides
1
.

befo re being used fo r p a rting In ord er t o p a rt silver fro m gold .

su c c essfully the f oll o wing points must receive c a reful c o nsider a

,

ti o n : ( 1) The strength of the a cid used ; (2) the temp er a ture of

t h e a cid ; (3 ) the r a ti o of gold t o silver in the h ea t o be p a rted d .

1 The pro per strength of a cid is o f grea t import a nce Fo r

d
. .

m erl y most a uthoriti es recommended th a t a cids of

,
an

sp gr —
respectively 2 p a r ts w a ter to 1 o f a cid g )
d d
. . sp r . .

a n 1 o f w a ter to 1 of a cid — b e used fi r st the we a k a ci d a n then ,

the stronger a cid T K R o se recommends 4 p a rts a cid t o 3

. . .

p a rts w a ter which strength if the a cid be he a ted will no t

, , ,

bre a k up t h e gold in t h e b ea d int o fine p a rticles even if 50 p a rts of ,

S ilv er a r e present to 1 p a rt o f go ld G old is l ess a p t t o bre a k up .

when it is l ess th a n mg in weight K ell er recommends

z
. .

1 C n l t th
o sup ti n S l ti n f G ld
“
e ca o b y HNO in Ch p t XI
o u o o o a er .

9
K ll T n A I M E XXXVI 3
e er , ra s. . . . .
, ,
1 08 A M AN UAL OF FI RE ASSAYIN G

a cid of the following st r ength : 1 p a rt a cid (sp gr to 9 p a rts . .

distilled w a ter In this strength o f a cid the gold a lm o st inv a r i

.

a bly rem a ins in a coherent m a ss even when the silver is 5 00 ,

times aS mu ch as the go ld This is the str ength of a cid reco m

'

mended fo r ordin a ry a ss a y purpo ses The be a ds sh o ul d b e b o il ed .

in the a cid for a t le a st 1 0 to 1 5 minutes in orde r t o insure p a rting .

2 It is essenti a l to h a ve the a cid a t the b o iling p o int bef o re

.
-

dropping in it t h e be a d t o be p a rt ed Putting the be a d into c old

d
.

a cid a n he a ting up gr a du a lly is a lmost cert a in to l ea ve t h e gold ,

especi ally where the r a ti o of silver t o go ld is high in a powdered

d
, ,

fine condition ve r y a pt to c a use loss es in w a shing a n subsequ ent

,

h a ndling o f the gold Cold a cid sh ou ld not b e us ed . .

3 While the best r a tio of silver to gold fo r p a rting ordin a ry

.
,

b ea d s is 5 to 1 this r a tio is no t al w a ys und er control since the

, , ,

a ss a yer must be content in m a ny c a ses with t h e r a tio th a t t h e

o r e fu r nishes him when this is m o re th a n 5 to 1 ,

If less th a n .

5 t o 1 silv e ,r sho ul d be a dd ed in o rder to bring it up t o this r a ti o .

The silver m a y be a dd ed directly t o the crucibl e or sc o r ifica t io n

fusion or t o the le a d butt o n during cupell a tion if it is no t
,

essenti a l t o det ermine the sil v er in the o r e

d
.

If it is essenti a l t o det ermine the silver a n inqu a rt a ti o n ,

is ne cess a ry the b ea d from t h e cupell a ti o n is fi r st w eighed the

, ,

dd
requisite a mount o f silver is a dded t o the b ea d b o th wr a pp ed up
d
,

in a b o ut 2 gr a ms of sheet le a d a n then it is r ecu p ell e a n ,

p a rted .

Be a ds which n eed inqu a r t a ti o n m a y a lso be fused with silver ,

o n a pi ece o f ch a rc o a l by me a ns of t h e bl o wpip e ; but this m eth o d

,

is not to be rec o m m end ed a s it frequently o cc a si o ns l o ss ,

.

Ma ny a ss a yers if th ey susp ect a n o re t o be defici ent in

d
d
,

silver for p a rting a silver t o the c r ucible not det ermining the
, ,

silver in this a ss a y but runni ng a se p a r a te sco r ifica tion a ss a y fo r

,

this purp o se
d
d
.

A no ther w a y is t o a
1
t o the ch a rge a desired number of cubic
centimeters o f A g NO3 soluti o n o f such st r ength th a t 1 c c . .

c ont a ins 1 mg A g The pro p er d eduction ca n th en be m a d e fro m

. .

the weight of the be a d but s o me a llow a nce must be m a de fo r ,

the silver a bso rb ed by the cupel .

d
A ft er p a rting the a cid is p o ured from the p a rting cup o r
,

fl a sk in which the oper a ti o n h a s b een conduct ed a n the gold ,

residue is w a shed a t l ea st three tim es with w a rm distilled w a ter

, ,

1F G H w l y E ng
. . ndM in J
a e X C 64 9
, . a . o ur .
, , .
1 10 A M AN UAL OF FI RE A ssA Y I N G

p a rt in fl a sks o r test-tubes it is essenti a l to h a ve the gold st a y a s

,

a coherent m a ss so a s to prevent lo ss in tr a nsference

,
When .

d
p a rting cups a r e used a fter w a shing the gold is c a refully dried
, ,

an the gold a nne a led a t a dull red h ea t either in the mu ffle o r

-
,

b yme a ns of the bl o wpipe .A fter a cid tre a tment the go ld is l eft ,

a s a s o ft bl a ck m a ss prob a bly a n a llotropic condition o f the go ld ;

,

but upon he a ting this is ch a nged to the norm al yellow met a llic
st a te in which it is weigh ed Fig 55 shows a c o nv eni ent p a rting
. .

b a th with test tub es ; Fig 56 shows p a r ting fl a sks c o mmonly in

- .

use .
 CHA PT E R I X
T HE ASS A Y OF OR E S C ONT A I NI N G IMPUR I T I E S

Impurities fro m the a ss a yer s point of view a r e such sub

,
’
,

st a nc es c o nt a ined in ores furn a ce products o r o ther m a teri a l

, , , ,

a s necessit a t e s o me p a rtic ul a r m ethod o f a ss a y o r tre a tment o r ,

the ob serv ing of speci a l prec a utions no t included in the o r din a ry

cruc i ble a ss a y as a lre a dy outlined .

Co mm o n impurities a r e sulphur a rsenic telluriu m a ntimony , , , ,

zinc copper etc Of these sul phur is by f a r the most c o mmon

, ,
. .

In perfo rming a n a ss a y it is usu a lly the a im of the a ss a yer ,

wh enever this is possi ble to produc e by direct fusion either by

, ,

the crucible o r sco r ific a tion method a pure le a d b utt o n weighing ,

a pproxim a t ely 20 gr a ms If the button is sm a ll er th a n this

.
,

d
there is d a nger of not collecting the v a lues ; if l a rger cupell a tion ,

is too prol o nged a n l o sses a r e incre a sed In the a ssa y of lo w .

gr a de gold ores it m a y be desira ble to pro duce l ea d buttons o f

25 to 30 gr a ms in o rder to obt a in the best results The impurities .

menti o ned a ff ect either the size of the butto n o r t h e purity of the ,

button or both T o S h o w the efiect of su lphur the following

, .

d efi nite e x a mple is t a ken .

G iven a n ore cont a ining pyrite which in a ch a rge yielding , ,

t h e o rdin a ry type o f m o n o si lic a te sl a g gives a reducing power ,

of 5 gr a ms o f le a d per gr a m o f ore If the f ollowing ch a rge .

,

1 5 g ra m s o f o re 70 g ra ms of Pb O
30 gr a m s of Ns zCO . 8 gr a ms of S iO ,

Bora x gla ss co ver

a e d
be m d up a n fused a 60 g ra m button ( a pproxim a tely) will be
,
-

d
produc ed on t o p of which will be a sm a ll qu a ntity of m a tte
, ,

i e a n a rtifici a l s ul phide of the met a ls in this c a s e iron a n le a d

d d
. .
,
.
,

This m a tte is b rit tle a n m a y cont a in so me silver a n a littl e gold

d
. .

On h a m m ering the butt o n it is l o st In gener a l it is a n u n esir

,
.
,

a bl e product t o m a ke A sm a ll a m o unt of m a tt e is p r o duc ed in

.

th is c a se since the ore h a s the p o wer to reduce 7 5 gr a ms of l ea d

,

from Pb O while only 7 0 gr a ms of Pb O a r e present so th at th e

, ,

111
1 12 A M AN UAL OF FI RE ASSAYIN G

e x c ess sulphide o f the o r e not a cted up o n by the Pb O rem a ins in

the ch a rge uni ting with some o f t h e le a d t o fo rm a sul phide of
d
,

iro n a n le a d The button is a ls o much t oo l a rge t o cupel If in

. .

the ch a rge the Pb O is m a teri a lly increa s ed the o r e will re a ct t o ,

the ex tent o f its full reducing power a le a d bu t to n o f 75 gr a m s

d
,

will be pro duced no m a tte will be found a n the sl a g will be

, ,

impro ved owing to the a dditi o n t o it o f t h e fusible b a se Pb O

,
.

If the Pb O in the ch a rge be m a teri a lly redu ced t h e l ea d butt o n ,

will be much sm a ller (o wing t o the d ea rth o f Pb O a v a il a bl e fo r

reduction) consider a ble m a tte w ill b eform ed a n the sl a g will
, ,
d
be poor .

If the sili ca b e incre a sed so th a t su ffici ent be present to fo rm

,

the high er silic a t es wi t h a ll t h e b a ses pres ent pr a ctic a lly no ,

le a d will b e r educ ed f o r t h e sulphid e h a s no t t h e p o wer to reduce

,

much Pb fr o m l ea d s o d a sili ca t es unl ess a fr ee b a s e be pres ent e g ,

. .
,

(Pb O N a 2
0 ).2 S iO2
FeS 2 ( no a cti o n),
or p o ssibly
2S iO2 + FeS , ZS iO2 Pb S S .

In this w a y t h e sulphur rem a ins in the ch a rge in the fo rm of

sulphid e sulphur .

S od a will c a use the f o r m a ti o n of S 0 3 if Pb O is p r esent t o

d
,

furnish the o x ygen a n if it c a n a ct a s a free b a se i e if it is

d
.
,
.
, ,

no t c o m bin ed with silic a (see Ch a pt er V o n R edu cti o n a n ,

Ox id a ti o n R ea cti o ns) A n in c rea se of s o d a with o ut a n in c rea se

.

o f Pb O or S iO2 will l ess en t h e a m o unt of m a tt e a s sulphur wi ll ,

t end t o c o mbine t o so m e ex t ent with the N a zO t o form with t h e

d
,

FeS a d o ubl e sulphide o f iro n a n sod a et c whi c h will b e dis

, ,
.
,

s olved in t h e sl a g The a b o ve o utlines t h e eff ect o f su c h impur

d d
.

iti es a s sulphur a n a r senic a n sh o ws t h e n ec essity of sp eci a l

d
,

m ethods o f a ss a y di r ect ed t o w a r d the getting r i of impurities .

T h e impuriti es m enti o ned m a y b e divid ed int o t w o cl a ss es :

( ) Those which b v l tiliz d by id ti n th rwis
d
a c a n e o a e o x a o o r o e e ,

e g
. . sulphur a rsenic a n a nti m o ny
, , ,
.

Th s whi h c nn t v l tiliz d c pper zin

d
( )
5 o e c a o b e o a e e g o c et c ,
. .
, , ,
.

S o m e of these m a y be p a rtly v ol a tiliz ed a s a nti m o ny a n ,

zinc Fo r t h e rem o v a l of a ll o f th em h o w ever wh eth er by

.
, ,

v ol a tiliz a ti o n o r by sl a gging o x id a ti o n is essenti a l ,

.

In o ne meth o d e m pl o yed on light sulphid e o r a r senic o nes

d
,

t h e ir o n n a il m eth o d sulphur a n a r s enic a r e c a r r i ed int o the

d
-
,

sl a g a s a d o ubl e sulphide o r a rsenide of so d a a n iron etc ,

.
1 14 A M A N UAL OF FI RE AS S AYIN G

S O, d
is discernible is c o oled a n mixed with 5 t o 1 0 gra ms of
d d
of ,

po wd ered ( N H, ) 2CO3 a n r er o a st e a t a lo w h ea t t h e sulphuric

, ,

a nhydride (S O, ) being elimin a ted a s v ol a tile a mmonium s ul ph a te ,

( N H.) 3 50 .

Cu so, ( N H,) , 0 0 , Cu O ( N H )
, ,
3 0 , 00 ,

ilver in the ore th a t h a s been roa sted will be in t h e form

d
A ny s

o f A g , S O, or if a rsenic a n a nti m o ny a r e present p a rtly in the

d
, ,

d
form of a rseni a tes a n a ntimoni a tes If the r o a sting temper a tu r e .

is c a rried to 8 70 C a n a b o ve the silver sulph a te will b e de

°
.
,

c o mp o sed le a ving the silv er in the form of met al lic silver In

, .

ord er t o a void l o ss of silver it is b est not to c a rry the temper a ture

a b o ve 700 C
°
.

In ro a sting simple pyrite ores the rea cti o ns a re si m il a r but

d
, ,

simpl er a n t h e temp er a ture ne ed no t be c a r ried a bov e 6 00 C

,
°
.

D uring ro a sting t h e o r e sh o uld be stirred frequently in ord er t o

,

expose fresh surf a ces t o oxid a ti o n

d
.

When o res c o nt a in a rs eni c a n a ntim o ny the ro a sting o p er a

d
ti o n is more di fficult a n c o mplex a n c o nsid er a bl e c a re a n , d
,

d
skill a r e required t o elimin a te the grea t er p a rt of th ese two vol a til e
el ements T h e re a so n fo r this is th a t t h e a rseni c a n a ntim o ny
. d
p a ss by ro a sting first to the st a t e of the l o wer o x ides A szOs
d
,

s s O which vol tile th n to the st t f the higher

d
,
a r e a a n e ,
a e o

o x ides A 8 2 0 ,” s Os f o rming a rseni a t es a n ,

a ntim o ni a tes o f cer

t a in met al s present in t h e o r e so me o f which a r e st a bl e ev en a t

d
,

high te m p era tures thus fi x ing the a rsenic a n a ntimony in t h e

d
,

roa sted o r e a n not elimin a ting it The a rseni a tes (o r a nti

d
.
,

mo ni a t es) which ordin a rily form a r e th o se of c o pper iro n a n

d
,

S ilver T h e b est c o nditi o ns fo r t h e eli m in a ti o n o f a rsenic a n

d
.

a ntimony a r e a ltern a te o x id a ti o n a n reducti o n a t a l o w h ea t

d
.

The presenc e o f sulphur tends to a i t h e elimin a ti o n of a rsenic

an d a ntim o ny by t h e f o r m a ti o n o f t h e v ol a til e sulphid es o f thes e

el em ents The reducing a cti o n nec ess a ry fo r th e elimin a ti o n of

d
.

a rs enic a n a ntim o ny is b est o bt a in ed by mi x ing with the o r e

equ a l v olum es o f c o a l dust o r ch a rc o a l a n ro a sting a t a d a rk r e ,

d d
he a t until t h e c o a l is burnt o ff then c ooling a dding m o re c o a l
d
, ,

dust a n r ero a st ing In t his w a y t h e gr ea t er p a rt o f the a rsenic

d
, .

an a ntim o ny c a n be rea dily v o l a tilized except in very rich ,

silver o res Wh en g a l en a ores a r e t o b e ro a sted the o r e is best

d
.
,

mi x ed with a n equ a l v olume of silic a a n ro a sted a t a very lo w

he a t In this ro a st Pb S O, is form ed to a consider a ble extent
.
,
 ASSAY OF O RES C O N TA ININ G I M PURI TI ES 1 15

whic h a t a higher h ea t is dec o mposed by the S iO, present , as

foll o ws
Ph sO, S iO2 Pb S iO, S O,
Ca re must b e t a ken with this ro a st a s a t the fo rm a tion p o i nt ,

of le a d silic a te silver losses a re a pt to occur A successful ro a st

d
.
,

will be indic a ted by a yellow c ol o r (l ea d silic a te) a n a n u nsu c ,

cessful o ne by a bl a ck or gr a y c o l o r (fused und ecom p osed sul

p h d
i es) In g.en e r a l he a v y sulphide,
o r es th a t cont a in their chi ef
,

v al ue in gold m a y be ro a sted wh en this is c a refully done without

, ,

l o ss of go ld ; but silver ores especi a lly wh en o f high gr a de a r e

, ,

a p t to give l o w results .

In m a king up the c h a rge for the ro asted ore it is to be no ted ,

th a t fro m a s ul phide o r e (pyr ite etc ) the pro duct is frequently

d
.
,

o f a n o xidizing n a ture a n b a sic which must be t a ken int o a cc o un t

,

in a dding the fluxes In g a len a ores when silic a h as been a dded

.
, ,

d
this must be a cc o unted fo r .

The ro a sting meth o d is frequently use fo r he a vy sulphide

o res especi a lly wh en th ey h a ve a lo w v a lue in g o ld a n
, silv er d ,

a s it p ermi ts of a l a rge a mount o f ore being t a ken ( 1 a ss a y t o n

an d m o re) wh ich af ter ro a sting presents no di ffic ul ty i n m a king

,

the pro per fusion .

T HE NIT E R M E T H O D — The fir st step in the ni ter method is the

‘

m a king o f a prelimin a ry a ss a y a cc o rding to the directions a lre a y d

given The prec a uti o ns concerni ng the reducing power of the
.

sulphides in di ff erent types of ch a rges must be c a refully no ted ;

it is b est to h a ve t h e prelimin a ry ch a rge of t h e sa me comp ositio n
a s t h e fin a l a ss a y ch a rge Or else the reducing power m a y be
d
.

d etermined by t h e s o d a -lith a rge ch a rge a n this cut d o wn by

d
d
25 per c ent 20 gr a ms deducted f o r the le a d button a n the
d
.
,

rem a ind er divided by 4 to get the a mount of niter to a in ,

gra ms if the m o no silic a te sl a g is to be m a de in the a ss a y

,
.

d
The a mount of o r e t a ken for the niter a ss a y v a ries a cc o rding t o
d
the gra d e o f the o r e in gold a n silver a n a cc o rding to the a mo unt
o f impurity present It is r a rely d esir a ble t o a m o re th a n d
d
d
.

20 gr a ms o f ni ter t o the ch a rge a s l a rger a mounts c a use ifli cul ty

,

thro ugh the ev oluti o n of t o o much g a s One h a lf a ss ay t o n - .

is the a mount o f ore most frequently t a ken S o metimes .

,

with o res cont a ining much impu r ity to a ss a y t o n is

,

us ed Twenty gr a m crucibles ( 1 70 c c c a p a city) a r e used fo r

d d
- .
. .

a m o unts o f a ss a y t o n of or e a n —
less a n 3 0 gr a m c ru cibl es ,

( 24 0 c c c
. a p a city.
) f o r 1 a ss a y t o n o f o r e .
1 16 A MA N UAL OF FI RE A S SAYIN G

MI LL E R ’
S OX ID
method is a mo ifie E -SL A G M E TH O D .
—This dd
niter m ethod a pplic a bl e t o such ores a s c o nt a in pr a ctic a lly no silic a ;
i e he a vy sulphide ores such a s pyr ites a rsenopyrite m a tt es
. .
, , , , ,

etc It is b a sed on the f a ct th a t Ph O h a s the power to hold in

d
.

so luti o n a n in suspensi o n oxides of such met a ls as copper iron , ,

“ ”
etc (see p 122 where scorifica tion is discu ssed) in cert a i n
d
. .
, ,

a mounts N iter is a dded t o oxidiz e the sulphides etc a n

d
. .
, ,

Na , CO, to a i in the complete oxid a tion of the sulphur by the

form a tion of sulph a tes in the m a nner a lre a dy discussed The ,
.

first st ep a s in the o rdin a ry ni ter m ethod is the prelimin a ry

, ,

a ss a y a ccording to the following ch a rge

,

Pb O
Na , CO3

The fin a l ch a rge is as foll ows :

0 5 a ssa y ton
gra ms
Na , CO, gr a m s
KNO 3 ( ca lcu a t e d fo r a 20-g ra m b utt on)

d
Q uick fires minutes found to be best The
d
1 1 00 C 3 0 a r e ,
°
.
, ,
.

sl a gs a r e usu a lly dull bl a ck a n pour re a dily a n the butt o n ,

sep a r a t es e a sily from the sl a g (In sl a gs high in silic a or co n

’

t a ining much b o ra x the le a d buttons a re a p t to a dhere cl o sely ,

t o the S l a g ) With the o xide sl a g met hod tro uble is sometimes

d
-
.
,

d
experienced through the le a d refusing to c o llect a n rem a ining
shotted thro ugh the sl a g The ifli culty is usu a lly u e to t o o . d
much sod a (esp eci a lly if c o nsider a ble niter is used) a lthough t o o

d
lo w a tempera ture of fusi o n is a lso a f a ctor .

The meth o d gives reli a ble results o n gold a n S ilver comp a r ,

ing well with the o ther st a nd a rd meth o ds 1

.

PER K I NS EXC E SS L IT HA R G E M E THOD

’ 2—
This method is b a sed
d
- .

o n the f a ct th a t Pb O will diss olve o x ides of o ther m et a ls a n if ,

p r es ent in gre a t excess will prevent to a l a rge extent the redu e

d
, , ,

ti o n of oth er met a ls such a s Cu a n S b The presence o f so , .

much Pb O a ls o insures a stro ngly oxidizing tende ncy in the

crucible preventi ng impurities entering into t h e button
d
d
.
,

It is desir a ble to a o r h a ve present S iO, in such a n a mount

a s will form a monosilic a te with the b a ses present including ,

1 Miller , H a ll an dF al k , T he R e d
uc t io n o f Lea fr om d l i th arg e, etc .
, in T r a ns . A . I .

M E XXXI V 398 3 99
dXXXI
. .
, , , .

3
W . G P kin T h Lith
. er s. e a rg e Pr o cess , ibi .
, , 9 13 .
1 18 A MA N UAL OF FI RE ASSAYIN G
TA BLE XX . A VE R AG E R E SULTS S H OWING E FFE CT
— OF A N
I NCR E ASE OF FD C O N S I L VE R R E SULT S

d
from Cob a lt Ca n a d a c o nt a ining cent N i
d d
An ore , ,
1
pe r .

an Co chi efly a s ni cc olite a n sm a lti t e

, , an some free
silver w a s a ss a yed by the following ch a rge :
0 05 a . t .

Na HCO , gra ms 10
10 gr a ms
1 5 gr a ms .

Litha rge a s gi ven in ta b le .

X X L A V E RA G E R E S ULT S SH OWI NG T HE EFFE CT

—

I NC R E ASE D AMOU NT OF PB O O N S I L VE R R E SULTS

T HE I R AI L M E T H O D This m eth o d d o es not a tte mpt

ON-N .
—

to o x idize impuriti es but a ims t o c a rry sul phur etc into t h e sl a g

d
. .
, , ,

The ore is decomposed by the iro n n a ils a dded t o the ch a rge a n

by the Pb O present A s iro n reduces Pb O to Pb the a mount of
.
,

lith a rge a dded t o the ch a rge is limit ed to 25 to 3 0 gr a ms The .

a mount of s o d a needed is l a rge a s this flux is depend ed u pon t o ,

c a rry the sulphur into t h e sl a g The sl a g should be below a

d
.

m onosilic a te in d egree a n h igh in sod a a s b a sic a lk a line sl a gs

, ,

h a ve a high solvent power for sulphides .

1 R . W . d
Lo g e. T h e E fiec t
'

of Hig h Li th a rg e i n th e Cr u cib le A ssa y for S ilver , T ra ns .

A I
. . M E . .
. XXXVIII . 63 8 .
 ASSAY OF O RES C O N TAININ G I M PURI TI ES 1 19

A typic a l ch a rge on a n ore th a t h as a reducing power of a b o ut

4 gra ms of Pb per gra m of ore is : 1

a ssa y t o n S iO,
30 gr a m s
30 gr a m s na ls i
S a lt co ver

The sod a sho uld usu a lly be twice t h e a mount of o re in the

ch a rge The re a ctions th a t t a ke pl a ce
. a r e a pproxim a tely a s

follows
7Ph O FeS , 4 Na HCO, 7Pb 2Na , S O, FeO 40 0 , 2 H, O

P a rt of the is d ecomp o sed by the Pb O a n p a rt of the S

o re ,
d
ma y g o off a s S O, a s di scuss ed in previ o us p a ges The iro n
,
.

n a ils decom p ose the b a l a nce o f t h e s ulphides :

FeS 2 + Fe = 2FeS
Pb s + Fe = Pb + FeS g a len a is present or le a d sulphide fo rm s)
(if .

The iron sulphide (FeS ) is disso lved by the a lk a line sl a g

d
,

forming prob a bly d o uble sulphides of sod a a n iron .

T o show the n a ture o f t h e iron n a il fu sion the f oll o wi ng -

,

results o f two fusions on a pyrite o re c o nt a ini ng per cent .

S — a —
reducing p o wer equ a l t o a b o ut 8 a r e g iv en z’

Ch a rge 1 Cha r ge 2
1 a ssa y t o n 0 5 assa y te n
3 0 gr a ms Na HCO 30 gra m s
Ph O 30 gra ms . .

4 g ra ms
4 na l s i
gr a m s 10 b or a x g la ss co ver . 10 gr a m s
The foll o wing results wer e o bt a in ed :

S la g
Ma tte
Lea d
d
Cr uc ib le a n c ha r ge befo re fu sion
d
Cr ucib le a n c ha r ge a ft er fu sio n
Loss in w eight .

Na i ls b efore fu sio n
Na ils a fter fusio n
Lo ss o f i ron
Per c ent o f S in sla g
.

S in sla g .

S in or e .

S pa ssed o ff a s S O,
S in m a tt e
d N
.

Lo p
d dp
1
g e, o tes o n A ssa y ing , . 99 .

Lo g e, ibi .
, . 1 01 .
120 A MA N UAL OF FI RE A S SAYIN G

It will be noted th a t the ch a rges a re identic a l a s fa r as the

fluxes a r e concerned but th a t the a mount of ore di ff ers It is
, .

d
desi r a ble in he a vy sulphide ores to keep the ore down t o
ass a y ton a n lower if necess a ry .

Ca re must be t a ken not to h a ve the sl a g a bove a monosili c a te

in degree for if higher in S iO, there will be p a rticul a r d a nger in
,

thi s ch a rge of not h a ving the sulphides oxidized by the Pb O ,

d
more sulphide being ret a ined in the ch a rge th a n it ca n dissolve ,

a n forming a m a tte even with sm a l l a mount of ore , ‘

.

T HE NIT E R IR ON M E T H O D
- — This method is in principle the
- a il
s a me as the iron n method A n a mount of niter i s a dd ed a t .

r a ndom su ffi c i ent to oxidize but a p ortion o f the sul p hides the
, ,

ba l a nce being dec o mpo sed by the n a i ls .

T HE C YA NI DE M E T H O D — S o metimes when no other fluxes a re .

,

d
a t h a nd or when a r a pid a ss a y is to be m a de in which a ccur a cy
,

is not essenti a l a fusi o n of o r e with cy a nide m a y be m a de a n

d
.
, ,

the res ult a nt button cupelled fo r silver a n gold The method

d
.

d
i s a r a pid one a n gives good m a lle a ble buttons but i s a pt t o be ,

d
l ow in gold a n silver especi a lly in silver The cy a nide u sed
,
.

shoul d be pure free from c a rb o n a tes or other impurities a n

, ,

the fusi o n should b e m a de a t a l o w temper a ture T he following .

ch a rge is used
to l y t on
a ssa

2 5 gr a ms
3 a ssa y t ons

al impuri doth r b se met

d
When the ore c o nt a ins copper a an e -

ties these a r e reduc ed a n enter the le a d button S ul phur is

,
.

t a ken up by the sl a g a s pot a ssium sulpho cy a n a te ( KONS ) In - -

.

gener a l it is a method not t o be recommend ed The following

,
.

1
results S how the loss in silver which t a kes pl a ce in this method .

TA B LE XXII .
— L OSS OF S I L VE R I N C YAN IDE ME T H OD

S il ver , by u ncorr ec te d a ssa y

S il ver in s a l g
S i l ver fr o m cu pel .

1 E H
. . Mill er , Co rr ec te dA ssa ys ,
”
in S ch M i nes
. Q ua rt XI X N , ovem ber , 1 8 97 .
1 22 A M A N UAL OF F I RE ASSAYIN G

the temper a ture empl o yed shoul d be low no t a bo ve 1 050 C ; ,

°
.

otherwise speiss (a n a rtifici a l a rsenid e of iron) is a p t t o form ,

which m a y c a rry v a lues It a lso h a s t h e obj e c ti o n in the c a se

.
,

of very impure ores th a t sm a ll qu a ntities must be t a ken fo r

,

a ss a y
,
involving serious ri sk of m ul tiplying a n error of a ss a y .

S CO R I FI CATION — This is the o x i dizing fusion of o r e with

.

met a llic le a d in the mu ffle furn a ce producing in the m a in a -

, , ,

lith a rge sl a g i e a n o xide sl a g It is a m eth o d o f a ss a y which

,
. .
,
.

d
requires no previous prep a r a ti o n o f the o r e o r prelimina ry a ss a y
d
,

an a s pr a ctic a lly o nl y o ne flu x is empl o yed it is both a che a p a n ,

a r a pid method It is a lso a th o ro ughly reli a ble m ethod when

d
.
,

pro per prec a utions a r e t a ken a n when it is empl o yed on m a

t erial suit a ble for t h e purpose T h e op er a ti o n is p e r f o rmed in
.

sh a ll o w fir e cl a y dishes c a ll ed sco r ifier s

-
,
.

The siz es comm o nl y us ed a r e

1 5 in
- . sc orifier s ; c u bic contents
2 0-in . sc o rifiers ; c u bi c co nt ent s .

2 5-in . sc o r ifiers ; c ubi c c o ntent s

3 5—in . sc o rifiers ; c u bic co nt ent s

The dimensions referred t o a re outside dimensions The .

size most commonly employed is the — in one Before . .

th ese dishes a r e used it is usu a l to line t h e inside with ferric

o x ide This is done by p r ep a ring cru shed iro n Or e or ochre
d
.
,

mixing with w a ter a n p a inting t h e inside o f t h e dishes This

d
‘

, .

gives them a b a sic li ni ng a n t o s o m e extent prevents the o xide

,

S l a g fro m a tt a cking the silic a in t h e cl a y .

S o me sco r ifier sl a gs especi a lly if they c o nt a in c o pper a r e

, ,

ve r y c o rrosive The a m o unt o f o r e t a ken fo r sco r ific a t io n

.

v a ries from a ss a y ton t o a ss a y t o n ; but a ss a y

t o n is the a mount m o st fr equently t a k en T h e l a rger a mounts .

a r e r a r ely used u nl ess the ore cont a ins pra ctic a ll y no b a s es

, .

S o m etimes for v ery impure m a teri al a s little a s

,
a ss a y ,

ton is t a ken The a m o unt o f t est l ea d v a ries a cc o rding t o the

.

n a ture of t h e ore The m o re im pu r e t h e o r e t h e l a rger will be

.

t h e r a tio o f l ea d to ore With a ss a y t o n t h e t est l ea d will

.

v a r y fro m 40 to 1 00 gr a ms A c o mmon ch a r ge is 4 0 t o 50 .

gr a ms of test le a d fo r o rdin a ry ores A s al r e a dy p o int ed out .

,

c ert a in qu a ntiti es of lith a rge a r e requi r ed in ord er to m a ke

fusibl e c o mp o unds with the m et al lic o xid es If the ore con .

t ains sm all a mounts of the met a llic oxide the test le a d will b e ,
 ASSAY OF O RES C O N T AINI N G I M P URI TI ES 1 23

s m a ll in a m o unt ; if it cont a ins a ppreci a bl e qu a ntities o f ferric

o xide (Fe3 0 3 ) o r Cu etc

d
d
l a rge a mounts of test l ea d will be r e
,
.
,

quired It is best t o a
. a sm a ll a mount of bor a x gl a ss to the

ch a rge fro m 1 to
,
gr a ms sc a ttering it over the surf a ce of ,

the lea d This a ids in the soluti o n of the b a ses p resent When
. .

the ore cont a ins the b asic oxides mentioned b o r a x gl a ss u p

d d
,

to 3 a n 4 gr a ms will m a teri a lly a i in forming go o d sl a gs ,

with o ut infusible scori a This infusible scori a o ften a ppe a rs

d
.

in ores c o nt a ining l a rge a mounts of b a ses a n is very a p t to ,

give lo w res ults by ent a n gling unfused portio ns of ore within

d
itself It is best t o mix t h e w eigh ed out portion of ore with
.
-

o ne h a lf of the test le a d to be us ed
- an then c o v er o v er with ,

t h e b ala nce .

The scor ific a tio n m a y be divided i nto t h e foll o wing distinct

d
steps
1 Melting In this st a ge the l ea d melts a n the o r e being
d
. .
, ,

o f a lesser gr a vit y rises to the su rf a ce of the m olten le a d a n

,

fl o a ts there .

2 R o a sting The or e o n the surf a ce of the l ea d is a tt a cked

d
. .

by the oxygen of the a ir a n ro a sts in the s a m e w a y a s de ‘

“
scribed und er R o a sting of Ores ”
.

3 S co r ifica tio n Proper The le a d c o mmences to oxidiz e

d
. .
,

fo rming lith a rge A sm a ll perc ent a ge (3 ) v ol a tilizes a n the

.

d
b a la nce forms a f usible sl a g This now a bso rbs the o x id es .

d
f o rmed by the ro a sting dissolving them a n forming a n igneous
‘

s oluti o n T h e silver a n gold li b er a ted a r e a bs o rbed by the

.
, ,

rem a ining met a llic le a d The sl a g a s it forms dro ps to the .

, ,

side forming a sl a g ring with t h e center of t h e le a d b a th open

, ,

t o the a tm o sphere The re a son for this is th a t the m eniscus of

.

m olten le a d is c onvex thus c a using the coll ecting o f the sl a g

,

o n the rim o f t h e sco r ifier T h e sco r ific a t io n c o ntinues until .

dd
the wh ole o f the l ea d is c o vered o v er with sl a g It is then co n
d
.

si er e finished a n the a ss a y is poured S hould the a ss a y be .

l eft in the mu ffle t h e l ea d will still c o ntinue t o o x idiz e a lth o ugh

, ,

none is exp o sed to the a ir the interc h a nge of oxygen t a king

d
,

pl a ce by m ea ns o f the lith a rge a n other o x ides present The .

size of the le a d butto n desired fro m this a ss a y r a fig es fro m 1 5

t o 20 gr a ms If the sco rific a tio n is c o ntinued to pro duc e
.

sm al l er b utto ns l o ss es a r e a pt to occur by o xid a ti o n of the

,

silv er esp eci a lly if this is present in consider a bl e a mounts thu s

, ,

forming rich sl a gs .
1 24 A M A N UAL OF FI R E ASSAYIN G

The temp er a ture o f sco r ific a tio n ra nges from 1 000 C to 1 1 00 °

.
°

C a lthough with pure ores b iger t emp er a tures m a y b e e m pl o yed

d
. .
,

When impure o res cont a ining much b a se m et a l a r e sco rifie ,

the butt o ns from the sco r ific a tio n a r e very a p t t o b e c o nt a mi

d
with b a se met a l especi a lly copp er a n wil l then h a ve d
d
na t e , ,

to be r esco r ifie with m o re test l ea d in order to get a pure ,

button for cupell a ti o n .

A ll met a ls a r e t o some extent oxidized simult a neousl y ,

but a mixture o f m et a l s m a y be ro ughly sep a r a ted by succ essi v e

.

o x id a ti o n e a ch m et a l in tu rn p a rti a lly pro t ec ting the m et a l

,

n ex t in o rd er while the l a tter m a y a ct a s a n o xygen c a rr i er t o

,

t h e forme r 1
T h e ord er o f o x id a ti o n is a s f ollows :
.

Fe t o Fe , O,
Z n t o Z nO
Pb t o Pb O
Ni to Ni O , ,

The o rd er of ox id a ti o n of the foll o wing elem ents is no t so

certa in

The ord er given in t h e t a bl e sh o ws the di fficul ty encountered

in t h e remov a l o f c o pp er by sco rifica tio n a s l ea d st a nds a hea d
d d
,

of it in the o rd er o f rem o v a l a n it is v ery di fficult a n requires ,

a number of r e sco rific a t io ns if the a m o unt o f c o pper is l a rge

-
, ,

to reduce it t o such a n a m o unt a s t o prevent loss in cup ell a ti o n

d d
.

Iro n a n zinc a r e ve r y rea ily remo ved by sco r ific a t io n (o x id a

t i o n) Cert a in el em ents lik e T e a n S e a r e difficult t o rem o v e d
d
.
, ,

fro m the l ea d button a n ma y tend t o c o nc ent r a te with the A u

d
,

an A g in the fin a l cupell a ti o n .

The sl a g fro m the sco rifica tio n a ss a y sh o uld b e hom o geneous

d
gl a ssy If it h a s a n e a rthy a pp ea ra nc e it is a n indic a ti o n
d
an .
,

o f t o o low a te m per a ture h a ving be en used an the butt o n is ,

a p t to b e brittl e due t o c o nt a ined Pb O Whit e p a tches o f

,
.

sulph a t e of l ea d o n the sl a g a fter pouring a lso indic a te r a ther

t oo l o w a te m per a tu r e of sco r ific a tio n a s this sulph a te f o rms a t ,

a l o w temp er a ture unde r sl o w oxid a ti o n .

The sco r ifica t io n m ethod is a reli a bl e o ne on most m a t eri a ls ,

with the ex c eptions enumera ted bel o w A s the usu a l qu a ntity .

T K R
1 . R fining G ld
. ose, B lli n t
e w i th O x yg n G
o in T n
u 1 M M A p il
o , e c .
, e a s, ra s . . . r .

1 905 .
1 26 A M A N UAL OF FI RE AS S AYIN G

m ethod fo r copper m a teri al Weigh out duplic a te s a mples o f

d
d d
.

1 a ss a y t o n ea ch o f c o pper b o rings a 3 50 c c cold w a ter a n

d
,
. .

10 0 c c HNO, (sp gr
. . an set in a c ool pl a ce for 20 h o urs
. .
,

stirring from time t o tim e Th en if the c o pper is not dissolved

d
d
.
, ,

a from 5 to 3 0 c c more of concentr a ted a cid A t the end of . . .

26 to 28 hours the soluti o n of the copper is complete D o no t .

a pply he a t in o rd er to minimize a s much a s po ssible the s o luti o n

o f sm a ll qu a ntities o f gold by wh a tev er a ction this m a y t a ke ,

pl a ce The o x ides of nitrogen in the solution a re removed by

.

bl o wing a ir into it fo r 20 t o 3 0 minutes .

S al t s oluti o n ( cont a ining gra ms of N a Cl per 1 000 c c ) . .

is a dded in su fi cient qu a ntity to precipit a te the A g present a s

chl o ride 1 c c of thi s solution will precipit a te 1 mg of A g
d
. . . .
,

a n excess o f 4 to 8 c c a b o ve th a t required for t h e A g sh o uld

d
d
an . .

be a dded If t h e a mount of A g in the c o pp er is sm a ll a 10 c c

d
. . .
,

d
o f a s a tur a t ed s oluti o n of le a d a cet a te a n 2 c c of conc entr a ted . .

H, S O4 in o rd er to fo rm Pb S O” to a i in settling the silver chlorid e

d
.

d
Let this st a nd f o r a bout 12 hours a n filter the precipit a te into

d
the pro per sized filter a n w a sh it well into the p o int o f the filter ,

p a per D ry the filter c a refully in the a ir b a th a n when dry

d
d d
.
, ,

a 8 gr a ms of t est l ead o n t o p of the precipit a te a n c a refully ,

tr a nsfer t o a scor ifier cont a ining 2 gra ms of l ea d This is pl a ced

d
.

d
in the mu ffle he a ted j ust t o incipient redness a n the fil ter
, ,

p a p ers burnt o fl but o nl y until the fl a me dis a ppe a rs a n no t , ,

into a sh This t a ke s o nl y a minute or so t h e prec a utio n being

.
,

t a ken to prev ent l o ss o f silver by v ol a t iliz a tio n a s A g Cl the le a d

d d
d
,

c a rbon present reducing the A g Cl t o A g Then a

d
an 3 to .

4 gr a ms o f Pb O a n the s a me a mount of b o r a x gl a ss r a is e t h e
d
, ,

he a t until well m olten a n pour No sco rifica t ion is necess a ry ,

.
,

d
a s no impuriti es a r e present The le a d button will weigh 5 t o .

d
8 gr a ms a n is cup ell ed with fe a th er lith a rge The results sho uld .

ch eck within oz for A g a n very cl o sely fo r gold 1

d d
to . .

S ul p hu ri c A ci M etho f or Blister Copp er fl To 80 c c of

—

d
d
. .

co ne H, S O, a
. 25 c c of a s olution of Cu S O4 ( 16 0 gr a ms p er . .

1 000 c c ) using a low wide N o 5 be a ker

. . H e a t t o such a t em . .

th t on the dditi n of the copper borings cti n com

d
d
p e r a t u r e a a o a o

mences immedi a t ely ; a 1 a t borings spre a ding them over the . .

,

b o ttom of the be a ker H e a t until a ll dissolving a ction h a s ce a sed .

,

W Liew in E ng a n M i n d J LXIX
d dM
1 R . . Van , . . o ur .
, , 4 98 et seq .

3
F F . . H unt ,
“
D ete r mi na tio n o f G ol in Co pper B ulli on,
”
E ng . an in . J oa n .
LXXX VII . 46 5 .
 ASSAY OF O RES C O N TAININ G I M P URI TI E S 1 27

usu a lly from 1 to 1 } hours ; then cool a n a 4 00 c c of dis dd

d . .

tilled w a ter stirring t o prevent c a king of the cryst a ls Bring t o

d
.
,

j ust a b o il filter a n wa sh the be a ker thoroughly using a ru bber

d
, , ,

ti pped gl a ss r e a s a stirrer Pl a ce the filter p a p er with the

d d
d
- .

residue in a in sco rifier dry a n burn o ff the p a per ; a

d
-
. 35 ,

gr a ms test le a d a n 1 gr a m sil ic a scorify t o a butto n of a bou t 9

d
,

gr a ms cu p el a n p a rt a s usu a l
, ,
.

S ilver m a y be d etermined by a dding s a lt solution a s in V a n

d
,

Liew s m eth o d a n 1 0 c c o f a 1 0 per cent solution of le a d a cet a te

d
’
. .
, .
,

dd
stirring well a n l etting st a nd over night Then filter with the
d d
.

d
usu a l prec a uti o n a n a the p a per a n precipit a te t o the s a m e
,

sco r ifier cont a ining the g old a n pro ceed a s in t h e c a se of gold ,

o nly .

In pl a ce o f cupric sulph a te mercuric nitr a te or mercuric ,

sulph a te
1
m a y be used the equiv al ent o f a b o ut 1 00 mgs of ,
.

mercury for a n a ss a y t o n of borings The mercury s a lt is best

d
.

a dded t o the copper borings stirring a little a n then a dding the

d
,

8 0 c c sulphuric a cid a n boiling on a h o t pl a te for three-qu a rt ers

. .

o f a n h o ur Then proceed a s a lre a dy d escrib ed When mercury

. .

sa lt is used in the a b o ve qu a ntity o n l o w gr a de bulli o ns c o nt a ining

-

from 1 0 t o 50 o z A g per t o n a ll the sil v er is thro wn down with the

.

d
gold If more silver is present s a lt soluti o n sh o uld be a dd ed in
.

suffici ent qu a ntity to precipit a te the silver a n a ny mercury !

th a t h a s p a ssed into soluti o n .

The o bj ect of the a ddition of cupric sulph a te o r the mercuric

d
s al t is to prevent the form a ti o n o f c o pper sulphides which will ,

rem a in in the residue a n m a ke necess a ry m o re th a n o ne sco rifi

c a ti o n to r em o ve t h e c o pper before cup ell a tion .

The s ul phuric a cid method is st a ted to give results equ a l to

-

”
the a ll fire meth o d (p 1 3 9) on gold . .

Combina ti on A ssa y f or M a tte — V a n Liew s m ethod of tre a ting

’
.

i n the cold is ra rely suit a ble for m a ttes a s he a t is usu a lly essenti a l ,

d
in o rder to insure a dec o mpositi o n of the m a tte in a re a so n a ble
length of time T a ke d uplic a tes of I a ss a y t o n e a ch a n tre a t
2
.

in l a rge b ea kers pro vided with w a tch gl a ss c o vers with 1 00 c c

d
- . .
, ,

of dis t ill ed w a ter a n 50 c c HNO, (sp gr A fter the

d
d
. . . .

d
vi olent ch emic a l a ction subsid es a 5 0 c c m o re of c o ncentr a ted ,
. .

a cid an
, w a rm the be a kers o n a hot pl a te until everything
soluble is dissolved : usu a lly residu e is white or gr a yish
the .
.

Flinn d
M J LXXXVII d
d pp M
1 F B
. .
, E ng . an in . our .
, , 5 69 ; a lso M in . an S ci . P r ess , CI . 1 48 .

“
3
A y ssa of Co pper an Co er a t t e,
”
in T ra ns A. . I . M E . XXV , 258 .
1 28 A MA N UAL OF FI RE ASSAYIN G

c o nsidera ble p a rt of the a c i d by b o iling ex

d
d
N ext ev a por a te a ,

pelling a ll o f the nitrous fumes d ilute to 500 c c a 3 c c of ,

. .
,
. .

concentra ted H, S O, 1 0 c c of sa tura ted le a d a c et a te s olution

d
,
. .
,

en o ugh s a lt s olution of the strength menti o ned for blister

d
an

c o pper t o precipit a te the silve r ; then stir briskly a n let them

s ta nd over night N ext m o rni ng w a rm the s olutions on a ste a m
d
.

b a th a n fil ter through r a ther thick filt er p a per

d
- .

F iltra tes must be perfectly cl ea r a n free fro m suspend ed

Pb S O, d
d
W a sh b ea kers a n residue th o ro ughly with hot w a t er
.
,

d
dry the filters in a n a ir b a th a n then wra p them up in a bout 8
d
,

gr a ms of sheet le a d a n sc o r ify with 4 0 gr a ms of test le a d a n

d dd
1 gra m o f b o r a x gl a ss Cupel the butt o ns with fe a ther lith a rge
d
. .

R e a ss a y the sl a g from the sco rific a tion a n the cup el a n a

d
—

the result a nt gold a n silver t o the a ss a y .

When he a vy c o pper ores a r e to be a ss a yed by this meth o d ,

which a re a p t to le a ve l a rge a mounts o f silici o us residu e the ,

genera l m ethod for m a ttes is foll o wed ex c ept th a t the residues

d
,

a fter filt ering a n drying a re trea ted a s foll o ws

T a ke a 20 g r a m cru cibl e a n pl a c e in it I a ss a y t o n of Ph O;
.
- d
then put the fil t er p a p er c o nt a ining the residue o n t o p of this
-
,

pl a ce the cru cible in t h e m o uth of t h e mu ffl e a t a l o w h ea t burn ,

o ff the fil ter p a p er until the fl a m e subsides rem o v e fro m the

d
-
,

mu ffle put a c o ver o n t h e crucible a n a ll o w t o c ool Wh en

d
d
.
, ,

cold a a ss a y ton Pb O 1 5 gr a ms o f N a , CO, 2 gr a ms of

d
, ,

a rgo l mix well with a sp a t ul a a n put o n a cover o f b o r a x gl a ss

, ,
.

Then pro c eed as in the o rdin a ry a ss a y

d
.

G ener a l Pr eca uti ons to be Obser ve i n the Combi na ti on A ssa y .

The combin a ti o n m ethods on co pp er m a teri al a gree well with the

st a nd a rd sco rifica t io n m ethods fo r the s a me m a te r i a l when co r
rec ti o n of cupel loss is m a de fo r the l a tter m eth o d The sc o ri .

fica tio n meth o ds will o ft en seem t o give high er r esults but this
d
,

is in mo st c a ses u e to the f a ct th a t the silver be a ds frequently

cont a in from to 4 per c ent cop p er T h e c o mbin a ti o n meth o d . .

gives in m o st c a ses ( V a n Li ew s meth o d p o ssibly e x cepted) ’

u niformly l o wer results in gold (4 per cent ) th a n t h e st a nd a rd .

corrected sco rific a tio n m eth o d This is gener a lly a scribed to the .

f o rm a ti o n of nit r o us a cid ( HN O, ) during s ol utio n which in , ,

c o nnecti o n with nitric a cid is s a id to h a ve a s olv ent a cti on o n ,

gold ; but such a uthorities a s W F H illebr a nd dispute this

1
. . .

W F Hi ll b ndnd C mp W et d Cr ucib le-Fi r e Meth o d

G ld
T llu id
1 . . E T A ll ne ra a . . e , o a r ison o f 3 . an s

O B l l 25 3 U S G S
”
for o e r e r es , u .
. . . . ur v ey .
13 0 A MA N UAL OF FI R E AS S AYI N G

1 mg . of s . d
ilver S tir b riskly with g l ass r o t o a gglomera t e the

d
silver chloride form ed
- .

The residues a r e then fil tered throug h the proper si z e fil ter ,

d
ca refull y w a shed with hot w a ter into the p oint of the fi l t er-p a per ,

dried in the a ir b a th a t a low he a t A fter drying tr a nsfer

d
an .
,

to a 20 g ra m c r ucible cont a ining 1 a ssa y ton o f li th a rge a n burn

dd
-
,

the fil ter p a p er OH in the m a nner a lre a dy described Then a

d d
- .

d
1 5 g r a m s of sod a a n 2 gr a ms of a rgol mix thoroughly a n
, ,

cover wi th a he a v y cover of bor ax

d
gl a ss Fuse a n cup el the
d
.

resul t a nt le a d b irtton Weigh th e gold a n silver b e a d a n

.
,

fro m a p reli min a ry assa y determin e the p roper a mo unt of s ilver

necessa r y in order to inu the h ea d The a mount of silver
.

shoul d be j ust a bout t i mes the a mount o f gold R oll out the .

be a d af ter fl a tteni ng with a h a mmer until a fter repe a ted

, , ,

roll i ng s the fillet will h a ve a bout the thickness of a v isiting c a rd

,
.

It is b e st to a nne a l the be a d a t a red he a t between the v a ri o us

roll i ngs in order to p revent cr a cking on the edges Then p a rt
,
.

in a p a rti ng fl ask i n h ot ni t ri c a cid h a ving a sp ecific gra vity of

Bo il twi ce for a t le a st 20 minutes e a ch time in ord er to ,

insu re the complete remov a of the silver This method of .

d
p a rti ng le a ves the gold in one coherent m a ss termed a cornet , ,

an is identic al wi th t h e method pra ctised in the gold b ul lion

 CHAP T ER X
SPE C I A L ME T H ODS OF A S S A Y

T E LL U R ID OR ES —
ores cont a ini ng the p recious met al s in
d
G old
d
E
the fo rm o f tellurides of gold a n silver m ainly c al a verite a n
d
,

sylv a ni te a r e m o re ifli cul t of a ss a y th a n ordin a ry gold ores

d
, ,

an speci al methods a r e essenti a l in order to get good r esults .

The scor ific a t ion a ss a y is not reli a ble for telluride ores g iving
d
,

al most u nif o rmly l o w results It is no t used by a ss a yers a n

.

chemists of t h e gre a t t ellurid e ore district in Color a do Cripple —

Creek It seems th a t in scorifica t ion the m a in c a use of loss is
.

v ol a tiliz a ti o n for while t h e sl a g l o ss is higher th a n fo r ordin a ry

d
,

ores sl a g a n cupel correcti o ns still le a ve the results fro m

,

this a ss a y fa r below tho se of the crucible a ssa y when pro perly

performed
d
.

Of recent ye a rs selenium g old ores h a ve been fo und a n in 1

d
gener a l the prec a utions necess a ry fo r the a ss a y o f telluride ores
a pply a lso to s elenium g o ld a n silver o res
d
.

Tellu r ium h a s a gre a t a ffinity for gold a n silver th a t for

silver b eing gre a ter th a n th a t for gold ; a n if a high gr a de d -

telluride or e be a ss a yed even by speci al method the be a ds fro m

, ,

the cupell a tion will frequently still cont a in tell urium 2

In the .

crucible a ss a y the losse s which a r e so mewh a t gre a ter th a n in

d
,

o rdin a ry ores occur in the sl a g a n fr o m the presence of t h e

, ,

Te in the le a d butt o n c a using a bs o rpti o n o f precio us met a ls

,

by the cupel The a im in the crucible a ss a y is to remove the

d d
.

tellurium from the gold a n silver a n sl a g it This is b est . .

a ccomplished by the presence o f c o nsider a ble lith a r ge a s a n o x i

d , d
izing a gent a n otherwise properly b a l a ncing the flux The .

flu x rec o mm ended quite gener a ll y by Cripple Creek a ss a y ers is

m a de up a s foll ows
Pota ssium ca r bona te 7 parts
S o diu m c a r b o na t e 6 p a r ts
B or a x gla ss . pa rt s
S l ni um G ld dM d
1“

dd
O X C, 4 1 8 : M i n a n S ci P r ess . 0 . 224
dO d
e e E ng o r e, . an i n J o ur
. .
, . . .

3 “
Woo
E . C . war , Cupel Losses in T ell uri e r es ,
"
in West Ch em a n M et , 1 , 1 20
. . . .

13 1
13 2 A M A N UAL OF FI RE ASSAYI N G

This is for the ordin a ry silicious Cripple Creek ores A b o u t .

7 5 gr a ms o f this flu x is used with a ss a y t o n of ore This g ives .

the foll owing ch a rge

Flou r

The he a t recom mended is such th a t a temper a ture of 1 063 C °

.
,

t h e melting point of go ld is re a ched a t the mouth of the mu ffle

-
, .

S ome a ss a yers recommend a s o m ewh a t gre a ter temper a t u r e to

insure the decompositi o n of the tell urides The time o f fusi o n .

should be a bout 4 5 to 50 minutes .

In most t elluride o res the silver c o ntents a r e no t gr e a t enough

to permit of the p a r ting of the be a d obt a ined fro m cupell a tion
d
d
.

d
It is th erefore nec ess a ry to a silver a t so me st a ge b efo re p a rt
ing a n in this inst a nce it is b est done du r ing the cru c ible a ss a y ,

since b y d o ing this th ere is a p t t o be l ess a bsorpti o n o f go ld dur

ing cupell a ti o n on a cc o unt of the presence of silver in t h e lea d

button .

It is essenti a l t o rec o gniz e th a t the flu x rec o mmended a b o ve

fo r t ellurides d o es no t m a ke wh a t c a n b e strictly termed a n
”
ex cess li th a rge ch a r ge
d
-
.

Hill ebr a nd a n A ll en recommend the foll o wing ch a rge fo r

1

Cripple Cr eek ores

Or e . Bo r a x gla ss gra ms
10
N s HCO , R e duc ing a gent (if nec essa r y )
Pb O S a lt cover

This a ppro a ches more nea rly the e x cess lith a rge ch a r g e -
.

The s a lt a s a cover m a y with a dv a nt a ge b e repl a c ed by lith a r ge

d
.

The fusi o n sho ul d be conducted slowly a n a t a temper a ture not

exceeding 9 50 to 1 000 C ° °
.

It is essenti a l in tellurid e ores t o h a ve the s a m ple crushed t o

1 20 or better t o 1 50 m esh
, ,
The re a so n for this is th a t owing
-
.
,

t o the irregul a r distributi o n o f v a lues in these ores fine crushing

d
,

is required to get a tru e s a mple a n a lso bec a use the lo w m elting ,

p oint of the ch a rge usu a lly empl o yed m a kes this essenti al
d
.

The precise b eh a vior of t ellurium in the crucible a ss a y a n dur ,

ing sco rific a t io n o r cupell a ti o n h a s no t a s yet b een investig a t ed ,

1 “
A Co m p a rison of a W et an d F
Cr ucib le- ir e Meth o d
s for th e A ssa y of Gol d T elluri d
e

Ores . B ull NO 25 3 , U S
. . . . G . S ur vey .
13 4 A M A N UAL OF FI RE ASSAY IN G

It will be noted th a t during cupell a tion the telluri um a t first

c oncentr a tes in the le a d a n th en begins to b e elimin a ted the d ,

p ercent a ge decre a sing In the c a se of sco rifica t ion th ere is a very .

decided c oncentra ti on of tell urium in the le a d tow a rd the end

o f the oper a ti o n The difference is pro b a bly due in l a rge p a rt
.

to the f a ct th a t in cupell a tion the t ellurium is in p a rt a bsorbed

b y the cupel a s a le a d tellurium a lloy which a cti o n c a nnot t a k e
'

pl a ce in sco rifica t ion The remov a l of tellurium by o xid a tion

d
.

d
from le a d thus p a ssing i nto cupel or sl a g is evidentl y a iflicult
d
, ,

process In a n a lloy of le a d gold a n silver a n tell urium t h e

.
, ,

d
tellurium ca n form compounds with both the preci o us met a ls
le a d It will be distributed b etween the two a ccording to
d
an .

the rel a tive m a sses p resent a n the rel a tive ch emic a l a ffinities .

d
If then in the a ll o y rel a tiv ely much le a d be present ( 1 00 t o 200
p a rts Pb per p a rt A u a n Te) by f a r the l a rger p a rt of t h e tellurium
will be elimin a t ed by a bso rption a s le a d telluride a n only a ,
d
little will st a y with the precio us met a ls This sm a ll a mount will .

no t be su fficient to m a teri al ly lessen the surf ace tension of the

be a d a t the end of the cupell a ti o n a n hence a bso rp tio n will b e d
sm all If h o wever the a m o unt of le a d be sm a ll so th a t the
d
.
, ,

rel a tive a mount of tellurium a n gold be incre a sed the a bsorption

o f the l a tter m a y be very he a vy It follows therefo re th a t in
1
.

le a d b uttons obt a ined in the crucible a ss a y which m a y cont a in ,

tellurium it is better to cupel directly in order to a v o id he a vy

,

a bsorpti o n in the cu p el S cor ifica t ion might b e res o rted to in .

this c a se fo r two re a sons : 1 To reduce a l a rge le a d button ; 2 . .

in the mist a ken ide a of elimin a ting tellurium .

F rom wh a t h a s gone b efore it is evid ent th a t a l a rge button

is not dis a dv a nt a geous a s it re al ly tends to decre a se the a b sor p
tion of preci o us met a l when tellurium is pres ent .

The preli m in a ry scorifica t io n of le a d butt o ns fro m crucible

a ss a ys o f t elluride ores h as b een S h o wn to giv e l OW l eS ll lt S The
z '
‘
.

c a u se fo r the al most univers al ly lo w results o n telluride ores

by the sco rifica t ion method is a ls o to be a ttributed in p a rt to the

d
a bove r ea sons .

4 S ilver seems t o exe r t a pr o tective a ction on the gold a n

.

lessen the a bso rption of the l a tt er due prob a bly t o the gre a ter ,

a fli nit y o f silver for tellurium thus forming silve r tellu r ide to the
‘
,

exclusion of the form a tion o f much gold tellurid e c o nsequently ,

R I
M M B ul 40
dW
K
d
1 T . . ose, T r a ns . . . . .
,

3
C . H F lt
. u o n, S choo l of M i nes ua r t Q .
, XIX , 4 1 9, an S . . S mi th . ibi .
 S P EC I AL M E TH O D S ,
OF ASSAY 13 5

l esseni ng the a bsorption of gold It is therefo re desir a ble to

.

perform the a ss a y in the p resence of consider a ble sil ver which

d
,

will h a ve t o be a ded a nyw a y a t a l a ter st a ge t o give a be a d th a t

will p a rt .

In the a ss a y of telluride ores t h e gener a l Obj ect therefore will

be t o remove a s much t ell urium fro m the gold a n sil ver before d
c upell a ti o n a s is possible This is b est done by the pe rform a nc e
.

o f a crucible a ss a y with a n O xidizing ch a rge T h e oxidizing .

properties of the cha rge a r e obt a ined by the use of a n excess of

lith a rge If we consid er the ordin a ry t elluride ore a s composed
.

o f a sil icious or sh a ly g a ngue cont a ining the p recious met al s a s

d
t ellurides a n c o nt a ining a lso c er ta in a mounts of sulphides the n ,

when this is subj ected to fusio n with lith a rge (a l a rge excess)
d
the telluride miner a ls a n sulphid es a r e o x idized the telluriu m ,

p ro b a bly forming tellur a te of le a d or in the presence of sod a , ,

tellur a te o f sod a (S ee beh a vior of sul phur Ch a p te r V ) If

. .
,
.
,

h o wever a n insu fficient a mount of Ph D is present so th a t it

,

f o rms le a d silic a tes onl y with the silic a of the ore the oxidizing ,

e ff ect will be much diminish ed since l ea d S ilic a tes f o rm a t a lo w

d
,

temper a ture a n do no t re a dil y give up oxygen It is therefore

d
.

esir a bl e t o fo rm a sl a g which h a s the ch a ra cteri stic s of a n

d
e x cess lith a rge ch a rge viz is not gl a ssy but o f a n e a rthy dull
,
.
, ,

a ppe a r a nce Consider a ble s o d a sho ul d be present to a i the

.

oxid a ti o n of the i m purities The bor a x gl a ss sh o uld not exceed

d
.

5 t o 1 0 gr a ms a n the le a d butt o n m a de sh o uld b e l a rge 25 t o 3 0

, ,

g r a ms The fusion should be m a de sl o wly p a rticul a rly a t first

d
.
, ,

an the temp er a ture not ex ceed a b o ut 1 000 C since there is a °

.
,

p o ssibility of disso ci a ting the tellurium compounds in the sl a g

d
an sending the t ellurium int o the l ea d button .

d d
It is pro b a bly impossible t o rem o ve a ll the tell urium from gold
a n silver by such a n o x i izing fusion for the re a s o n th a t the r e

d uction of le a d from s o me of the lith a rge a t a cert a in st a ge of the

a ss a y f o r t h e collection o f the g o ld a n d
silver a lso a g a in reduces ,

so me o f the tellurium which h a s been oxidized It is desir a ble to .

o bt a in the full oxidi z ing eff ect of t h e lith a rge before t h e reducti o n

d
d
o f l ea d t a kes pl a c e a n for this re a son ch a rc o al is to be r ecom
mended a s the reducing a gent when this needs to be employe, ,

inste a d of a rgol or flour S ince the CO evolved b y the two l a tter

,

b egins to reduce Pb from Ph O a t a bout 3 00 C less th a n s oli °

.
d
c a rb o n which a c ts a t a bout 550 C (p a ge
,
°
.
13 6 A M A N UAL OF FI RE ASSAYIN G

ordin a ry sili c ious telluride ores o f o nly slight reducing

Fo r
po wer t h e fo llo wing ch a rge is rec o m m end ed
Or e, a . t .

Ph O, g r .

Na , CO, , 30 0 g r .

Bora x gla ss , g r .

Cha r coa l ,
1 1 g r .

S il ver foi l ,
1 0 to 20 mg s .

P h O c o ver , 10 gr .

The fusion sho uld be c o nducted slowly a t first the fin a l tem ,

p e r a t u r e no t much exce eding 1 000 C °

.

If th e butto n fro m the fusion is th o ught t o c o nt a in tellurium ,

a s is p r o b a bly the c a se in t h e a ss a y of a high gr a de o r e it will be

-
,

d
desir a ble t o pl a ce it in a 20 gra m crucibl e c o ver with 3 0 gra ms
-
,

Pb O mixed with 2 gra ms b o r a x gl a ss a n b r ing t o fusion then

d
, ,

pour a n proc eed a s usu a l This tre a t m ent will elimin a te co n

d
.

si er a b l e t ellurium from the l ea d (S W S mith ) . . . .

It is st a ted th a t in t h e o x idizing ro a sting of Crippl e Cr eek

d
1

t elluri de ores in th eir prep a r a tion for chl o r in a ti o n o r cya ni a

,

d
ti o n the gre a ter p a rt o f the tellurium in the r a w or e is found in
d
,

the ro a sted ore a s a t ellurite of iron S ome a ss a yer s a a n ir o n .

n a il t o the a ss a y not so much t o d esulphurize a s t o provide a n

,

excess of iron fo r the purpose of combining the t ellurium with it ,

a s in the c a se of sulphur .

Fo r the qu a ntity of tellurium pres ent its influence on the ,

a ss a y is c er ta inly p r of o und The foll o wing t a ble gives a n ide a

.

o f the qu a ntity present :

TA B LE XXI V .
—
Q UAN T I TY OF TE LL UR I UM I N OR E S

lre a dy st a ted t ellurium is with di fficulty sep a r a t ed fro m

d
As
d
a ,

gold a n silver a n in S pite of a n o xidizing ch a rge is frequ ently

,

c a rried down in the le a d button The loss then t a kes pl a ce in .

the cupel tell urium c a using a h ea vy a bs o rption S o m e loss

,
.
,

howev er t a kes pl a ce by vol a tiliz a tion There is a lso a somewh a t

,
.

1 T n
ra 1 M M III 49 50
s . . .
, , .
13 8 A M A N UAL OF F I RE ASSAYIN G

Three a ss a y to ns of flux w ere used to e a ch a ss a y t o n o f

or e with a s o d a cover one qu a rt er inch thick A ss a ys were m a de

-
.
,

in qu a d r uple a ll fusions b eing s a lted with A g p a rted in 1 t o 4

d
, ,

a cid a n the be a ds required t o ch eck a g a inst ea ch o th er in weigh t

an d
,

then weighed t o gether a n the sum divi ed by 2 t o get t h e

v a lue p er t o n .
,
d d
The stock flux is equiv a lent to the following ch a rge
Or e 0 5 a ssa y to n Pb O
N a CO , , 9 gr a ms B or a x gla ss
K CO , 6 gr a ms A r go l

results of these series of ass a ys were as foll ows

LOT N o .ASSA Y E R A ASSA YER B
Oz A u p er t on
. Oz A u p er t on
.

88870

0 80 0 88

88890
7 1 95 7

3 84 3
8 8780
22 522
9 8509
22050

A ss a yer s A dthen e B
ch a nged fluxes a n a s they checked
an x ,
d
ea ch o th er s previ o us results cl o s ely it b ec a me evid ent th a t the
’

d
,

d
flux of a ss a yer A w a s ill b al a nced a n wo uld no t give go od results
-
.

S l a g a n cupel corrections were m a de by A ss a yer A on a ss a ys

m ade with his flux but ev en th ese c o rrecti o ns a dded f a iled t o
,

bring his results up to those of a ss a yer B .

The questi o n a rises a s t o wh a t is the specific tro uble with

flux A On e x a min a tion it will be found t o cont a in a n excessive
.
,

a mount of b o r a x gl a ss especi a lly when the c o v er is considered

,
.

It is very prob a ble th a t the a cidity of the ch a rge (a lth o ugh a go o d

fluid sl a g is obt a ined) is so gr e a t t a king into a ccount both the
d
,

silic a of the ore a n the b o r a x gl a ss th a t the ore is no t co m ,

 S P EC I AL M ETH ODS OF A SS AY 13 9

l l dec mposed by the b sic i n re ients of the ch a rge ; i e d

d d d
p et e y o a g . .
,

t h e sod a a n lith a rge b ecome s a tur a ted with b o r a x a n then o

not completely d ec o mp o se t h e silici o us o r e The f a ct th a t t e .

a ss a ys of the sl a g do not bring the results up t o t h e figures o b

d
,

t a ine by a ss a yer B doe s not necess a rily imply th a t the sl a g do es

not cont a in these v a lu es a s the c h a rge used to flu x the sl a gs a n
, d
c upels a g a in cont a ins much b o r a x gl a ss so th a t pr a ctic a lly t h e ,

sa me c o nditi o ns obt a ined a s b ef o re .

T HE A SS A Y OF C OPPE R B E A R I NG MAT E R IA L — Co pper be a r

d
- - .

ing m a t eri a l includ es o res c o nt a i ni ng co pp er a n furn a ce pro ducts ,

c hiefly m a tt es blister c o pp er et c Copp er which in the a ss a y

, ,
.
,

h a s a stro ng t end ency t o g o int o t h e l ea d butt o n c a uses wh en , ,

p resent in su ffici ent qu a ntity se r i o us losses by cupel a bsor ption , .

Th erefo re a ll m eth o ds of a ssa ys fo r this cl a ss of m a t eri al end ea v o r

t o elimin a te c o pp er from the l ea d button t o b e cup ell ed A .

st a nd a rd m eth o d fo r the a ss a y of m a te r i a l high in copper espe

d
,

cia ll y fo r A g is the c o mbin a ti o n a ss a y for blister c o pp er a n

,

d
m a ttes describ ed in Ch a pter I X
d
.
,

A n o ther st a n a rd m eth o d especi all y f or go ld a n one th a t , ,

is c a rried o u t frequ ently a s a check t o the a b o v e is t h e sco rific a ,

f

tio n or a ll fir e m ethod This is p erfo rm ed a s foll o ws

”

d
.

T en s a mpl es of a ss a y ton ea c h a r e t a k en a n
,
pl a ced in ,

3 inch sco rifier s with 50 gr a ms of t est l ea d (the silver c o nt ent o f

-

which is a ccur a tely known) ; 25 gra ms of t h e le a d a r e mixed with

t h e m a tte or borings etc the oth er 25 gr a ms us ed a s a d
d
,
an ,
.
,

c o ver On t o p of the ch a rge is pl a c ed 1 gr a m e a ch of silic a a n

b ora x gl a ss The sco r ifica tio n is c a rri ed on a t a m o d er a te t em
.

until the ss ys j ust bout sl g over which t k

d
p e r a t u r e a a a r e a t o a a es ,

usu a lly a b o ut 25 m inutes a n then they a r e p o ured T h e result

d
.
,

a nt butt o n will w eigh a b o ut 1 5 t o 1 6 gr a ms a n be quit e h a r d

with copp er T h e butt o ns cl ea ned from sl a g a r e sc o rifie test
.
, ,
d
,

le a d being a dded t o m a ke the t o t a l l ea d up t o 40 gra ms The

d
.

second sco r ific a tio n will t a ke a b o ut 30 minutes a n the result a nt

butto ns will w eigh fr o m 1 0 t o 1 2 gr a ms Th ese a r e cup ell ed in .

1 0 s ep a r a te cup els pl a c ed so a s to be subj ect t o unif o rm tem

’

t i in h riz nt l cross h mu ffl C ll
’

p e r a u r e
,
e . o n e o
.
,
o a r o w a t e e u p e a .

ti o n sho uld b e conduct ed a t a s l o w a t emp er a tu r e a s is f ea sible

d
.

The be a ds a r e w eighed sep a r a tely a n then t o gether They -

.

a r e then gr o uped in two lots of 5 e a ch which a r e p a rt ed in a cid ,

,

strength 1 t o 9 the be a ds being k ept in this a c id a t n ea rly b o iling

d
,

t empera ture for 20 minutes a n finished fo r 5 minutes with

1 40 A MA N UAL OF FI RE ASSAYIN G

gr a cid (full strength)

sp . . T h e ten cup els a r e t a ken in lots .

d
o f t w o e a ch (o nl y the lith a rge st a ined p a r t is t a ken)
- crushed t o ,

p a ss 1 00 mesh a n a ss a yed by the following ch a rge

-

1 00 gr a ms Pb O 45 gr a m s bor a x gla ss
20 g r a ms Na , CO 3 gr a m s a r gol
S o da co ver

The le a d buttons a r e cupell ed a n the silver a n gold o bt a ined ,

d d
T h e scor ifica t io n S l a gs m a y a lso be
dd
a dd ed t o the fi r st weights .

r ea ssa ye an this corr ecti o n a dd ed but in pr a ctice the cupel ,

c o rrection is the o nl y o ne usu a lly a ll o w ed S ometi m es no co rree .

ti o n is a ll o wed It is t o be no ted th a t even with a r esco r ifica

.
,

tio n of the first button of the a ss a y the fin a l sil ver be a ds from

d
, ,

55 per cent Cu m a tte c o nt a ining 1 8 0 o z A g p er ton a n

. oz . .

d
gold will cont a in fro m
, to 4 per cent copper which must be .
,

educted in order to get c o rrect silver resul ts (Fo r a fu r ther

d
.

discussion of sco r ific a tion sl a g losses a n cup el a bsorpti o n in

a ss a ying copper-be a ring m a teri a l see Ch a pt er X I ) ,
.

The sco rifica tion m ethod is gener a lly e m pl o yed fo r the d et er

min a ti o n o f gold in m a ttes a n the c o mbin a ti o n m eth o d fo r t h e ,
d
determin a tion of silver Of recent yea rs speci a l crucibl e m eth o d s
d
.
,

f or c o pper m a ttes a n copper be a ring m a teri a l h a ve been d evel -

o ped with consider a bl e succ ess

1
.

A s a tisf a ct o ry method o n copper m a ttes up to 20 per cent

d d
.
,

c o pper a n high in gold a n silver w as pr a ctised by t h e S t a nd a rd ,

S m elting Co mp a ny a t R a pid City S Da k T h e m a tte s a m pl e

d
. .
, ,

is put through a 120 mesh screen a n fo r controls 4 a ss a ys of -

,

a ssa y ton e a ch a r e m a d e with t h e f o ll o wing st o ck flux : ,

1 1 p a rt s S o dium ca r b o na te 2 5 pa r t s .

70 p a r t s Nit er 5 p a rt s

An ss a y t o n m a tte is ru n w ith a
a a ss a y t o n flu x a n d
a thin b o r a x gl a ss c o ve r The flu x figured . t o the ch a rge is a s
follows
0 25 a ssa y t o n m a t te
gr a m s S iO ,

g r a ms Pb O

The he a t used is high a n the fusi o n sh o rt giving a cl ea n d

d
,

d
fluid sl a g a n a bright butt o n of a pproxim a tely 20 gr a ms These
d
.

buttons a r e cupelled directly for gold a n S ilver One cupel a n .

1 “
A n A ll-fir e M eth o for th e ssa d A y of G ol dd
S an il v er in B lister COp p er ,
”
in T r a ns .

A I M E , XXX III
Per ki ns, T h e Li th arg e Pr ocess for th e A ssa y of Co pper

ibid
. . . . 6 70 .

b ear ing O r es .
"
XX XI .
, , 91 3 .
14 2 A M A N UAL OF FI RE ASSAYIN G

TA B LE XXV I I . C OR R E CT E D A N D U NC OR R E CTE D ASSA YS

O N COPPE R MA TTE

Cruc ible m eth o d

R efiner
Co m p a ny
Lo t No .

A typic a l s a mple of m a tte on which these a ss a ys were m a de

a n a lyzes a s follows

4 10. oz .
p er ton p er cent .

oz .
p er ton p er c ent .

p er c ent .
p er cent .

p er c ent . tr a c e
2 5 p er cent .

The crucible ch a rge employed c a n re a dily be m o dified t o

a pply to m a tt es higher in copper or gr ea t er in reducing p o wer .

Perkins e x cess lith a rge m ethod h a s a lre a dy b een d escribed

’
-
.

H e st a tes th a t fo r lo w gr a de copper be a ring m a teri al (2 to 4 p er

- -

5 a ss a y t o ns of Pb O to a ss a y t o n of o r e will rem o ve

most of the c o pp er if the b a l a nc e of the flu x es is pro p erly

,

proportioned i e if the r e is a mple free Pb O t o disso lve c o pp er

,
. .
,

o xides . Fo r high gra d e m a ttes et a

- — 4 8 to 60 p er cent copper,
.
 S P EC I AL M ETH O DS OF ASSAY 1 43

— 8 ss a y tons of Pb O t o
a a ss a y t o n o f m a tte will remove mos t

o f t h e c o pper Perkins a lso d evelop ed a crucible method for

.

m et a llic c o pper a s foll o ws : ,

Weigh out a ss a y t o n of c o pper borings divide it into

d
,

3 a ppro x im a tely equ a l p a rts a n pl a ce in 20 gr a m c ru cibles

- In ,
.

this w a y weigh out 4 sets getting 1 2 a ss a ys Into e a ch crucibl e ,

.

put 8 00 mgs of powd ered sulphur mix th o roughly with t h e

d
.
,

c opper an,
th en o n top o f this put t h e foll o wing flux being ,

c a reful no t t o mix th e fl ux with t he c o ppe r

0 25. a ssa y ton

0 25. a ssa y to n
S a lt c o v er

Pl a ce t h e c r ucibles into a d k r e mu m e a n gr a du a lly r a ise ar -

d d
the temp er a ture fo r 4 5 minutes t o a yell o w he a t T h e t empera
d
.

tu r e regul a ti o n is imp o rt a nt a n it is necess a ry t o pro duce a ,

neutr a l o r r educing a t m osphere in t h e mu ffl e by the p r esenc e of

co a l or c o ke The butto ns w eighing a bout 1 8 gr a m s ea ch a r e
d
.
, ,

put together in l o ts of thr ee representing

d
a ss a y t o n a n , ,

sco r ifie The result a nt butt o ns sho uld w ei gh

d
a t a l o w h ea t .

5 t o 6 gr a ms E a ch of these buttons is no w r esco rifie with

.

25 gr a ms of l ea d a t a low he a t until 6 gr a m butt o ns a r e obt a ined ,

- .

Th ese a r e cup ell ed with fea thers This m eth o d is st a ted t o give
d
.

results o n go ld equ a l t o the a ll scorifica tio n method a n o n silver -

/
,

equ a l t o t h e c o mbin a tion meth o d 1

.

T HE A SSAY OF Z I NC I FE R OUS OR E S AN D M E TALL U R G I C

PR OD U CT S C ONTA I NI NG Z I NC — Z inc m o st fr equ ently o ccurs
d
.

in o res a s the sulphid e sph a l erite a n in c er t a in m et a llu r gic al

, , ,

pro ducts a s th e met a l (zinc cy a ni d e precipit a t es) Z inc b o ils a t

d
.
,

d
9 4 0 C a n r a pidly v ol a tiliz es Z inc o xid e v o l a tiliz es sl o wly a t
d
°
. .
,

Z inc silic a t es a l o ne a r e ifficu ltly

d
an r a pidly a t
fusibl e but a r e rea dil y so when mi x ed with b o r a x o r b o r ica ci
,

o r f er ro us S ilic a t e The presence of zinc in m a teri a l to be a ss a yed

d
1
.

c a lls fo r c ert a in prec a uti o ns a n in gene r a l the a ss a y is di fficult

d
.
,

Met a llic zinc h a s a grea t a ffinity for gold a n silv er grea ter th a n ,

le a d a s is sh o wn by the P a rkes pro c ess f or th e d esilveriz a ti o n o f

,

le a d bulli o n U nder oxidizing influ ences the fo rm a tion of zin c

d d
2
.

o x id e a n its v ol a tiliz a tion c a uses losses o f gold a n silver Th a t .

this l o ss is mech a nic a l d o es no t m a ke i t less seri o us The b o il .

R R fi ni ng G d O xyg G as . i n T r a ns 1 M M Ap il
d
1 o se . e ol B ullio n, etc .
, in en
”
. . . .
, r , 1 90 5 .

3
Willia ms , in J o ur Ch em Met . . . an M in S oc
. . o f S o u th A
frica , III
, 1 32 .
1 44 A M A N UAL OF FI RE ASSAYIN G

ing p o int of z inc occurs a t a temp er a ture somewh a t bel o w t h e

d
-

n o rm a l for ordin a ry sco rifica tion a n it is this f a ct coupled with , ,

the f a ct th a t the zinc o xide formed is with di fficulty soluble in

lith a rge th a t m a ke a ccura te a ss a y results h a rd to obt a in especi a lly
d
-
, ,

in scor ific a t io n Z inc cont a ining gold a n silver m a y be distilled

d d
.

o ff a n vol a tilized with very little le ss of gold a n S ilver i f the ,

conditions a r e reducing 1
.

S co rific a t ion is frequently employed fo r zinciferous ores ,

a lthough it is no t gener a lly s a tisf a ct o ry When used it is b est .

,

c a r ried out in a w a y simil a r t o tha t a d o pted for c o pper be a ring -

m a t eri a l using from a ss a y t o n of ore with from

d
, to
50 t o 8 0 gr a ms of test le a d 2 gr a ms of b o r a x gl a ss a n 1 gr a m , ,

o f silic a the l a st being essenti a l t o flux the zinc oxid e form ed

d
,
.

Otherwise I ns oluble sc o ri a a n crusts f o rm on t h e sco rifier Sla g

d d
.

an cupel c o rrecti o ns a r e genera lly necess a ry a n from 5 to 1 0

a ss a ys a re m a de the results being a ver a ged A S zinc is re a dily
,
.

o x idized le a d buttons cont a min a ted with zinc a r e no t t o be fe a red

d
,

an r esco r ific a t io n is r a rely necess a ry A mong t h e most im .

p o rt a nt zinciferous m a teri a l presented for a ss a y a re the zinc gold -

'

precipit a tes fro m the cya ni de p ro c ess S co r ific a t io n is no t de .

”
sir a ble fo r these They a r e best a ss a yed by the crucible meth o d
.

o r by one o f t h e co mb ina t ion methods a lre a dy described

d
.

Cr uci ble M etho — The crucibl e meth o d b est suited fo r u nox

dd
.

i ize zinc o res is the ni ter m ethod with su ffici ent S ilic a pres ent
d
,

t o form a t le a st the monosilic a t e with zinc Bo r a x gl a ss a n .

much lith a rge is a lso desira ble On a pr a ctic a lly pure sph a lerite .

the foll owing ch a rge will give good fusi o ns a t temper a tures of
a b o ut 1 1 00 C
°

Ore . 0 5 a ssa y t o n S iO 8 gr a ms ,

Na CO , , 15 gr a ms KNO 2 2 gr a m s ,

1 50 gr a ms Hea vy bo r a x gla ss co ver 3

d
.

This ch a r ge c a n b e modified a s reg a rds niter a n silic a t o , ,

suit a ny sph a l er ite o r e .

A good cruci ble ch a rge fo r cy a nide precipit a tes cont a i ni ng up ,

t o 50 per cent zinc is .

,

Pr ecipit a t es 0 1 a ssa y t on S iO .
2

Na CO , , 5 g r a m s N a B O , ,
.
,

Pb O 70 gr a m s F lou r
Light bor a x gl a ss co ver
1 R ibid ndf
ose , n .
, a r e er e ces .

“
N t n th A y f Z in P ipit t Q u t XX II 1 53
dby Lay f mpl x zin -l d n nt t ; see
3
in S h l f M i n
mm nd
o es o e ssa o c rec a e s, c oo o es ar .
, ,
.

3
A imil h g i
M i n I nd
s ar c ar e s r eco e e , or co e c ea co ce ra e

. XIII 287
. . . .
1 46 A M A N UAL o r F I RE ASSAYI N G

In b oth methods it is essenti a l th a t the a mount o f p ul p ,

d
u su a lly should not exceed
, assa y ton the c a rbon givin g ,

i fficul ties with g re a ter a mounts th a n this

d
.

T he A ssa y of R esi ues fr om Z i nc Distilla ti on (conta i ni ng con

d
si er a ble ca r bon) f or S il ver a n G ol 1—
F rom a ss a y dd
d
to .

t o n of the p owd ered residue is mixed with 35 gr a ms of niter a n

1 0 gra ms of Na , o, (sodium p ero xide) a n dro pped in l o ts of
°

,
d ,

d
5 gra m s e a ch into a red h o t c r ucible which c a n be re a d ily c o vered
-
, ,

an the oxid a tion rea ctions p er mitted to complete themselves .

The flux then a dded co nsists of 70 gra m s of lith a rge 1 0 gra ms of

d
,

b or a x gl a ss 1 0 gra m s silic a 2 gr a m s a rgol a n a light bor a x gl a ss

d
, ,

c over The fu sion is c a rri ed out a t a yell o w h ea t a n the buttons

.

c upelled a s usu a l .

T HE ASS AY OF A NTI M ONIA L A ND A R S E NI CAL OR E S FOR

G LD
O A ND SI LV E R -G old a n s ilver be a ring a ntim oni al ores
- . d ,

such a s stibnite j a meso ni te etc a r e usu a ll y a ss a yed by t h e

d
.
, , ,
.

”
ni ter method in the presence of consider a ble so d a a n niter t o
, ,

induce the form a tion of the a ntimo ni a te of sod a A prelimin a ry .

a ss a y to determine the a mount of nit er is ess enti al The follow .

ing ch a rge i s recommended fo r ne a rly p ure stibnite : 3

a ssa y ton KNO 8

1 20 gra ms Bor a x gla ss .

10 g ra ms S iO,
S a lt co ver

The fusion should be conducted slowly a n a t a lo w tempera d

ture The button will usu a lly c o nt a in very little a ntimony the
. .
,

cupel not showing sc o ri a o r cr a cks If it d o es cont a in en ough

d
.

t o c a use lo sses in cupell a ti o n the butt o ns sh o ul d be sc o r ifie ,

.

S mith gives the f o llowing ch a rge fo r ore cont a ining a p

‘

p roxim a tely 75 per cent stibnite The nite r etc c a n be . .

,
.
,

v a ried for the ore a s the g a ng ue incre a s es :

Or e 1 a ssa y ton 8 gra m s
Pho 7 5 g r a ms 2 0 to 2 5 g ra m s
Na , CO.

meth o d pr a ctic a lly a s go o d a s the niter meth o d is

A n o ther , ,

the ro a sting with ch a rco a l or c oke dust

- “ The s a mple of ore .
,

K S ndin E M nd M i n J w n LXXIII 3 80
Willi m Kitt T h A y of A ntim ni l G ld
1 a er , a o
. . .
, , .

“ O I M M 1 906 N 8
d
in T
"
a o , n e ssa o a o res , ra s . . . .
, , o v.

d
an Dec 1 3 . .

S mi th , T h e ssay of Co mple G olA x O ”

I M M IX
d
res . in T r a ns . . . .
, , 33 2 .

S mith , (bi .

S ulma n. T r a ns 1 M M 1x , 3 40 . . . .
 S P EC I AL M ET HODS or ASSAY 147

u su a lly I a ss a y ton is mixed with a pproxim a tely its own volum e

,

dust pl a ced in a 5 in ro a sting dish c o ver ed

d
o f c ok e dust o r co
- al -
,
- .
,

with a no ther dish a n ro a sted in a mu ffle with cl o sed d oo r

d
, ,

a t a tempe r a ture no t exceeding a d a rk cherry r e (6 3 5 fo r - °

a b o ut 3 5 t o 4 0 minutes This wil l c a use the v ol a tiliz a tion o f

.

95 t o 96 p er cent of the a ntim o ny a s sul phide with o ut a ppreci a ble

.

loss of gold The ro a st sh o uld h a ve a yellow a ppe a r a nce when

d
.

finished a n c a n b e f used with the fo llowing ch a rge :

,

S iO,

B or ax gla ss c o ver

This meth o d gi ves good resul ts on j a meso nit e o res .

A rsenic a lores a re a ss a yed by the s a me meth o ds a s the a nti

mo ni al ores ; a lso by the iro n n a il method a lthough this l a st is -
,

not gener a ll y to be rec o mmended The subj ect of the best

d
.

method of a ss a y of a ntimonia l a n a rsenic al ores still l a cks

th o ro ugh i nvestig a tion The chief points ma y be outlined a s
.

follow s :
1 In the ro a sting u nl ess gre a t c a re i s t a ken a s reg a rds
d
.
,

d
tempera ture m ech a nic a l l oss o f gold a n silver t a kes pl a ce
, ,

owi ng t o the r a pid diseng a gement of the a rsenic a n a ntimony

oxides or sul phides of these met a ls Unl ess the ro a st is con
d
, .

ducted a t a lo w he a t a n in the presence of c o nsidera ble c a rb o n

d
,

a rse ni a tes a n a ntim o ni a tes o f b a se met a ls or silv er m a y form ,

h olding v a lues which l a ter on a r e not compl etely d ec o m p o sed in

the crucible owing to their st a b il ity a t a high t emper a ture the
, ,

resul t being a ppreci a ble sl a g l o sses .

2 In the niter method the presence of much niter with its

.
, ,

powerful oxidizing eff ect ma y a lso i nduce t h e fo rm a ti o n of

a rseni a tes a n d
a ntimo ni a tes c o nt a i ni ng silver a n
,

p o ssibly gold
,
d ,

which will rem a in in the sl a g .

3 In the iron n a il method u nl e ss t h e fluxes a r e c a refull y

d
-
.
,

d
a dj usted a n the temper a ture kept bel o w 1 1 00 C speiss c a r rying
°
.
,

v a l ues is very a p t to form a b o ve the l ea d button a n thus neces ,

sit a te a r e a ss a y or a tre a tment o f this speiss

-
,
.

T he A ssa y of A r seni ca l Ni ckel coba lt S ilver Or e 1—

T w o type s
d
-
.

o f o res m a y be c o nsidered 1 Those high in A g a n a l so high

d d
. .

in Ni a n Co contents a n 2 those lo w in A g but hi g h in N i

,
.
,

1 D . K . B ullens, E ng . an d
M i n J o a n , X C, 809
. . d
Lo g e. T r a ns. AI . . M E
. .
. X XXVI II
'

,
1 48 A M A N UAL or F I R E A SS AYIN G

an d
0 contents
0 It is essenti a l to flux the N i a n Co in the sl a g
. d
since these element s seriousl y interfere with cu p ell a tion c a using
lo w results N i present in the le a d button t o the a mount of
.

0 5 per cent c a uses a scum of M O to b e left on the cupel

. . More .

“ ”
th a n this c a uses the freezing of the button The effect of .

cob a lt is not so pronounced as th a t of nickel .

For the o res high in silver the scorifica tion a ss a y is to be

recommended with the following ch a rge :

to 0 10. a . t .

65 t o 75 gra m s
3 to 5 g r a ms
1 to 3 g r a ms

Sl a g an d
cupel corrections sh uld be m de o a . It is desir a ble at

times to check results by w et a n a lysis for silver .

Fo r ores lo w in silver the crucible a ss a y with high lith a rge

gives better results th a n the scorific a tion a ss a y S m a ll a mounts
d
.

of o r e ,
a t sho uld be used , for the nickel c o b a lt a n
. .
, ,

a rse ni c in the ores a r e a pt to f o rm a speiss in the a ss a y F or .

“ ”
ores c o nt a i ni ng met a llic silver in a ny a mount the sc al e a ss a y
sho uld first be m a de .

T HE A SSAY OF S U LPH ID E S M AI NL Y PYR I TE BU T CON , ,

TAI NI NG S M ALL A M OUNTS or COPPE R Z I NC S U LPHI D E S ET C , , .

—Where gold only h a s t o be determined in o res of this ch a r a c

ter the ro a sting method is s a tisf a ctory This however pro ves
d
, .
, ,

unreli a ble for silver a n in m a ny c a ses (a s a t Le a dville) the silver

,

contents o f these sulphides a r e the m o st import a nt The best .

method a fter m a ny tri als w a s found to be the niter fusi o n o n

, ,

comp a r a tively sm a ll lots of ore The ore h a s the foll o wing .

a na l ys1s :

3 3 t o 44 per cent . 4 t0 8 per c ent .

3 8 t o 4 5 p er c ent . 0 5 to 3 5 p er
. . c ent .

4 to 20 p er c ent . 0 to p er c ent .

F our a ss a ys a re m a de on a ss a y ton e a ch with 3 t o 4 ,

a ss a y t o ns of the following flux the a mount depending on the ,

r educing p o w er ; i e on the a mount of s ulphides p resent :

. .
,
1 50 A M A N UAL OF F I R E ASSAYIN G

of pyrite will reduce a 22 gra m button F or every 5 per c ent . .

o f pyrite present a bove 1 5 per cent gra ms of niter a re neces .

,

sa ry t o destro y the excess reducing power T w o stock fluxe s a re .

d
u sed in the a ss a y o f ores 1 The reducing flux designed t o g ive
. .
,

a 22 g r a m button with a neutr a l o re on a ch a rge o f a t ore a n . .

a me asure o r scoop of flux (8 4 gr a ms) This flux is m a d e a s .

follows : Pb O 1 5 p a rts ; Na , CO, 4 p a rts ; bor a x 2 p a rts ; flour

, , ,

p a rts When 84 g r a m s of flu x a re u sed this gives th e

.

following ch a rge :

Ph O .

Na , CO.
B or a x

2 . N on reducing flux to be used in connectio n with nite r for

-

sul p hide ores which w ill g ive a butt o n l a rger th a n 22 gra ms .

Thi s flux is m a de a s follows : Pb O 1 5 p a rts ; N a , CO, p a rts ; ,

bor a x p a rts ; silic a p a rts When 84 gr a ms of this flux .

a r e u sed it gives the following ch a rge :

a ssa y t on
g rams
Na , CO, gra ms
gra ms
gra m s
A s nec essa ry

d
When sulphid e ores a r e a ss a yed which do not cont a in su fficient
sulphide s for a 22 gra m button the reducing a n non reducing ,
-

fluxes a re mixed in such proportion a s to obt a in the correct result .

—
Thus suppose a n o re cont a ins 1 0 per cent pyrite its reducing .
,

power would be gr a ms le a d on the b a sis of

a t The deficiency in le a d is therefo re 22
. . gr a ms .

d
In order to obt a in gr a ms le a d the following a m o unt of re
u cing flux is required : gr a ms The b al a nce .

of the ch a rge of 8 4 gr a ms will be ma de up of non reducing flux

d
-
,

an t h e whole ch a rg e will be :

Ore
R ed ucing flux .

Non reducing
- flux

The fluxes dter ni me a sured by volume in pro p erly

d
an a re

esi ned scoo p s

g or me a sures .
 S P EC I AL M E T H O DS OF ASSAY 15 1

For high sul p hide ores when very a ccur a te resul t s a re require d
a prelimin a ry a ss a y is m a de a s follows :
Or e .

Non-r ed u cing flux 50 0 g r a ms

This is run in a 1 0 gra m cr u cible This ch a rge w ill g ive a .

le a d button weighing a s much a s the niter necess a ry t o oxidize

a ll the sul phides in a t o f the o r e Pl a ce t h e le a d butt on
d
. . .

obt ained in one sc a le p a n of the p ul p sc a le a n from t h e hoo k -

a bove the other p a n su spend by fine wire a weight so th a t with t h e

wire it a mounts to 6 gr a m s Then a niter to the p a n h a ving the

. d
d
6 gr a m weight u ntil the sc a le i s i n b a l a nce This a mou nt of .

niter is the proper a mount necess a ry to produce a 22 gr a m butto n

d
with the ore a n the non reducing flux i f
- a t o f o re is t a ke n . .

for a ss a y (Consul t Ch a pt er V )
. .

d
F or import a nt a ss a ys it is desi r a ble t o m a ke 4 assa ys combine ,

the buttons fro m 2 a n sco rify into one button ea ch Ma ke

,
.

the t w o cupell a tions weigh t h ebe a ds sep a r a tely for A g combine

d
, ,

them for p a rting a n m a ke one weighing on gold .

If the ores ass a yed cont a in mo re th a n 1 2 per cent cop p er i t is

d
.
,

desira ble to t a ke the le a d butto ns fro m the ass a y a n pl a ce them

into crucibles with 50 gra ms of lith a rge a n 2 gr a ms S iO, pl a ce d
d
,

in the mu ffle a n le a ve there four o r five mi nutes a fter the Pb O

d
d
h a s melted Then withdr a w the crucible a n wi th the to ngs
.

give the contents a r a pid swi rli ng motion for a few minut es a n
then pour This tre a t ment elimin a tes most of the co pp er r e
d
.

m a ining in the button Then cupel a n p a rt a s usu a l It is t o

. .

be noted th a t the method s described ma y h a ve t o be modified

t o su it p a rticul a r conditions .

T HE ASS AY OF MA T E R IA L CO NTAI NI NG M E T A LLIC SCA L E S

d
.

— Ores of this kind a r e di ffit to a ss a y a n obt a i n corr ect r e

sult s from a s the met a llic p a rticles (usu a ll y gold or silver) a r e so
,

unevenly distributed a s to m a ke it pra ctic a lly im p ossible t o oh

d
t a in a n a ccur a te s a mple T w o met hod s of a ss a y a re a v a il a ble :
.

( ) A pproxim tely gr ms ore ( less if deemed i

dd
a a 5 00 a o f o r a v s ,

a ble) a r e weighed o u t crush e ,

an put through a 1 50 or 200
,

m esh screen c a re being t a ken t o sep a r a te ou t the sc al e s a s closely

d
,

a s possible S creening a n crushing sh ou ld frequently succeed

.

d
e a ch other When a ll the sc a les h a ve been sep a r a ted out they
.
,

a r e tr a nsferred to a p a rting cup a n dissolved in 3 to 5 c c of . .

nitro hydrochloric a cid if gold o r in nitric a cid if silver or copper

-
, ,
.

The pulp is then he a ped up into a cone in a l a rge p orcel a in dish ,

1 52 A M A N UAL O F F I R E A S S A YI N G

t he gold etc s olution poured on the a pex o f the cone a n t h e

,
.
, , d
p a rt ing cup w a sh ed ou t thoroughly with w a rm distilled w a ter ,

using no more th a n is ne cess a ry t o c o mpletely w a sh it o u t The .

bed o f pulp should b e thick enough to r e a dily a bso rb all of the

,
d
soluti o n a n not p ermit it to p enetr a te to the dish The pulp is .

th en dried in a n a ir b a th a t 1 20 C thoroughl y mi x ed o n gl a z ed
d
°
.
,

p a per a n put through the screen repe a tedly It is then a ss a yed

,
.

by the method suit a ble to it like a ny other o re ,

.

d
( )
b F rom to gr ms f w ighed crushed
d
2 00 5 0 0 a o o r e a r e e o u t ,

d
a n screen ed a n the sc a les sep a r a ted a s d esc r ibed a b o ve The
d
.
, ,

sc a l es a n the pulp a re then weighed a n t h e l o ss in dusting

n o ted The sc a l es a r e a ss a yed by sco rifica tio n; t h e l ea d button
d d
.

i s cupelled a n the be a d weigh ed a n p a rted Then 1 5 gra ms

,
.

d
o f the o r e is w eighed o u t in duplic a t e fused with t h e prop er ,

ch a rge the l ea d butt o ns fro m these fusions cupell ed a n the

d
, ,

be a ds weighed a n p a rted F rom the results obt a ined the tot al

d
.
,

d
silver in the o rigin a l o r e is c a lcul a ted con
d
a mount of go ld a n

d
,

d
si er ing b o th pulp a n sc a les The g old a n silv er respectively
d
.
, ,

found is multiplied by an ivid ed by the o r igin a l weight

of ore t a ken in g r a ms ; this g ives the v a lue in ounces p er t o n
,
.

T HE ASSA Y OF OR E S CONTAI NI NG T H E I R CHI E F VA LU E

I N FR E E G O L D — A s a lre a dy point ed o u t these o r es a r e di fficult
.
,

to g et c o rrect r esults fro m E ven th o ugh t h e free gold p a rticles

.

a r e very fine it is i m p o ssible to distribute them unifo r mly

,

through o ut the bulk of the s a mple The p r o per w a y to a ss a y .

m a teri a l of this kind is to t a ke from 1 000 t o 1 500 gr a ms of

the ore c r ush ed through a 1 00 m esh screen pl a ce in a
,
-
,

l a rge M a s o n j a r with a tight screw cov er mix t o a r a th er thick

d d
d
,

pulp with w a t er a n th en a 3 t o 4 c c of mercury fro m . .

a b u rette It is essenti a l th a t the m ercu r y sh o uld be free

d
.

from gold a n silver or its c o nt ents o f preci o us met a ls

,

known Mo st mercury a s purch a sed c o nt a ins so me gold The

d
.

j a r a n its c o nt ents a r e th en a git a ted f o r t w o h o urs best in ,

some m ech a nic a l a git a t o r Then c a r eful ly s ep a r a t e the mercury

.

fro m t h e ore by p a nn ing in a gold p a n s a ving a ll the pulp in , ,

a nother p a n o f s o mewh a t l a r g er size N one of the fine slimes of

d
d
.

the o r e must be p erm itted t o esc a pe It m a y be nec ess a ry t o a

d
.

a little m o re mercury a n a v ery little s o dium a m a lg a m during

p a nning to coll ect a ny floured a n sickened mercury The pul p d .

d
is a llowed to settle in th e p a n the su r plus w a t er c a refully p o ured
d
,

o ff
, an the p a n then set on a h o t pl a te to dry When ry it .
1 54 A M A N UAL OF F I R E ASSAY IN G

G rind for a few minutes a n then w a sh the silic a a n a c i d 0 6 d d

with w a ter a n proceed a s b efore d .

A M AL G A M ATIO N T E S T T O DE T E R M I N E T HE A M O U NT OF
“FR E E ” G O L D PR ES E NTS — One hundred gr a m s of crushed
into a citra te of m a gnesi a b o ttle 1 50
d
o r e a r e weigh ed o ut ,

c c of w a ter a dded a n then 2 c c of pure mercury from

d
. . . .

d
a burette The sto pper is cl a mp e
. the b o ttle rolled in a ,

piece of cl o th a n pl a ced in a moving sh a ker for t w o h o urs .

d
It is then removed op ened covered with the thumb sh a k en
d
, , , ,

an inverted over a 3 in p o r cel a in dish a n a s much cle a n .

,

d
mercury a s p o ssible al l o wed to run out A little more w a t er .

is a dded a n more m ercury a llowed to r un ou t into a no ther

d
dish a n so o n a s l o ng as a ny com es out If the mercu ry .

is not floured ne a rly a ll is rem o ved in t w o oper a ti o ns A ll .

d
the cl ea n m ercury is then put into a 250 c c be a ker The . . .

bottle is then sh a ken well a n a g a in inv ert ed t o let a littl e

‘

sand run out into a dish This s a nd is then p a nned into a n .

en a meled dish usu a ll y only a few gl o bul es of mercury being

,

d
obt a ined If much is found from this third inversion the whol e
.

ch a rge must be p a nned a n if the mercury is fl o ured a sm a ll glob

ul e o f liquid sodium a m a lg a m sh o uld be a dded to the p a n .

In ordin a ry r o utine work the t a ilings fro m the p a nning a r e

disc a rd ed Fo r speci a l purp o ses a s w hen the t a ilings a r e t o b e
.
'

tested by cy a niding c o nc entr a ti o n etc th ey a r e a ll o w ed t o

d
, ,
.

s ettle c o mpletely d ec a nted a n if nec ess a ry dri ed fo r further

,

tests or fo r a ss a y T o the m ercury a fter its coll ec ti o n in t h e

.

250 c c b ea ker r m f pure silver is dded if this h been

d
. .
g a o a ( a s

c a refully prep a red a n cl ea ned by tre a ting in cy a nide soluti o n o r

we a k nitric a cid or by slightly a m a lga m a ting the surf a ce it
m a y be used to pick up th e sm a ll gl o bul es o f mercury collect ed
in p a nni ng) a bout 1 50 c c of E NOs sp gr previ o usly
. .
,
. .

w a rmed t o a bout 70 C is now poured into the be a ker which is

°

d
.

set into a n en a m el ed p a n on a hot pl a te a n left there till a ll

the mercury h a s diss olved If no t t oo h o t it is unnecess a ry t o .

c o ver the be a ker A s soon a s the mercury dis a pp ea rs the liquid

.

is filtered o n a cm p a p er previ o usly w etted The residue

. .

is rinsed o n to the p a per w a sh ed o nce or twice with very dil HNO,

d
.
,

( n o t o v er 5 p e r cent ) a n once with w a t er .T es t l e a d is then .

sprinkled o n t h e p a per it is folded pl a ced o u t est le a d in a

d
'

, ,

sco r ifi er a n en o ugh l ea d a dded t o m a ke a 20 gr a m butt o n .

M th d d
1 e t th H m t k Mi n S D
o use a e C mm ni t d
o by Wm J S h w d
es a e e. . . o u ca e . . ar oo .
 SP EC I AL M ET H O DS OF ASSAY 1 55

S ilver is a dded to insure p a r ting a n a lso a few gr a ms of b o r a x d

gl a ss The scorifier i s then ch a rged into the m u ffle the p a per
d
.
,

burned the ch a rge sco rifie for a few minutes poured the
d d
, , ,

button cupelled a n the be a d p a rted a n t h e gold weighed .

From a 1 00 gr a m ore s a mple e a ch mg of gold represents .

o z or
. free gold p er ton .

Notes on the Ca rr yi ng Ou t of the A ma l g a ma ti on T est — The a m a l

g a m a t io n test is c a rri e d out for the purpose of determi ni ng the
a mount of pre cious met al s th a t ca n be recovered from the o r e

in milling oper a tions by me a ns of a m a lg a m a tion The size of the .

crush ed ore will influenc e the resul ts ; therefo re in di ff erent tests ,

the degree of fineness must be n ea rly c o nst a nt The ex a ct fine .

ness used depends upon conditi o ns Tem p er a ture h a s its influ .

F m 57 — Ho M E S T A x
. . E A G IT A I OB F O B
' ‘
A M A LOA M A T I ON AND CY A N I D E T E S T S .

ence ; if the tests a r e c a rried out a t tempera tures high er th a n the

norm a l d a il y temper a ture resul ts will be higher If th e t empera .

ture be lo w resul ts will be lower The a ddition of silver to the .

m ercury reduces the time r equired for its solutio n by a b o ut o ne

h a lf E x treme c a re must be t a ken to g et m ercury a n silver
. d
d
p r a ctic a lly free from gold It is desir a ble t o run a bl a nk a ss a y
.

o n sa y 20 c c o f mercury a n 5 gr a ms of silver (representing ten

d
. .

times the qu a ntity of e a ch used in the a ss a y) The mercury a n .

d
silver a r e dissolv ed in a cid a s st a ted in the a m al g a m a ti o n test

a n the residues tre a t ed a s desc ribed The best mercu r y obt a ined
d
.

a fter testing a numb er of new fl a sks a n when used with commer

d
c ia l proof silver required a c o rrecti o n of mg o f gold fo r 2 c c . . .

d
mercury a n gr a m silver The silver c o nt a ined ne a rly h al f
.

of the g ol thus found If the a mount of silver in the o re

.

recover a ble by a m alga m a ti o n is to be determ ined the p a rting

of the mercury by nitric a cid must be repl a ced by the crucibl e
1 56 A MA N UAL OF F I RE ASSAYIN G

f usion of the mercury a s described in method 1 for the a ss a y of

ores cont a ini ng free g old
d
.

E qu ip ment R equ ir e f R i A m l m T
d
or o u t ne a g a a ti on ests .

1 S h a king b o x with 24 c o mp a rtments e a ch 3 in squ a re a n

. .

6 in deep a s shown in F ig 57 The foll owing a r e the det a ils

d
. . .

of construction S id es a n bottom m a de of
. in lumber ; .

p a rtitions of in lumber ; sills 4 X 4 in lumber ; connecting rod

. .

Ii X i in o a k lumber
1 4 ft long ; supports of light steel 1 5 X 1 ¢ §

d
. . .
,

in a n 2 ft long ; sh a ft 1 in 250 r p m ; throw of eccentric

dd
. . . . . .
,

2 in A fru e v a nner eccentric r o a n su p ports m a y be used in

d
.

the const r u ction of the a git a to r A p a sh o uld be pl a ced a t the .

bottom of e a ch pocket Pieces of c a nton fl a nnel 12 t o 1 5 in .

,
.

squ a re a r e used to wr a p e a ch m a gnesi a bottle

,
.

2 Twenty-four citr a te of m a gnesi a bottles with spring cl a m p s

d
.

an rubber w a shers These h a ve a c a p a city o f 3 50 3 70 c c

.
— . .

3 Twenty four be a kers c a p a city a bout 2 50 c c

.
-
,
. .

4 T w o en a meled iron p a ns to h old 1 2 be a kers e a ch

d
. .

5 S ix porcel a in dishes 3 in in di a meter a n 2 en a meled iron

d
. .
,

p a ns 8 in in di a m eter a n 2 in d eep
,
. . .

6 Filtering r a ck fo r 1 2 2% in fun nels Twelve extra be a kers

d
.
- . . .

7 Co pp er weighing sco o p a n c o pper funnel with steep sides

.

d
for ch a rging b o ttles .

8 Cylinder gr a du a ted to 1 00 1 50 a n 200 c c

.
, ,
. .

'

9 G l ass stopper burette st a nding in en a m el ed iron p a n

. .

1 0 S upplies a s mentioned in the a ss a y

d
. .

T HE ASS A Y OF CYA NI D E S O L UTIO NS M etho — Me as ure .

o u t a ny c o nve ni ent v o lume int o a be a ker (pref er a bly 1 0 or 20 a t

d
d
.

using be a kers of 500 to 700 c c c a p a city) A 1 0 to 20 c c of . . . . .

le a d a cet a te solution cont a i ni ng 1 0 to 20 per cent of the s a lt then .

,

introduce 3 to 4 gr a ms of zinc dust in the form o f a n emulsion or

suspension in w a ter a n st a nd on a hot pl a te When modera tely d .

he a ted but before b o iling a cidify with a bout 20 c c strong ,

. .

d
hydrochloric a cid either c p or of the best commerci a l gr a de
,
. . .

Bo il until a cti o n ne a rly ce a ses a n the redu ced le a d h a s c o llected

”
,

d
d
int o a spongy m a ss Filter o n a quick p a p er a n w a sh pre .
,

cipit a t e twice with hydr a nt w a t er R e move the fil t er p a per a n

d
-
.

d
p recipit a te a n squ eeze out a s much w a ter a s possible Pl a ce .

in a 2 in sco rifier wi th 1 0 to 1 5 gr a m s of t est l ea d a n 3 to 5

.

d
gra ms of bor a x gl a ss Pl a ce a t once in t h e mu ffle burn the p a per
.
, ,

scorify for o nl y a few minutes pour cupel le a d button p a rt a n , , ,

D ue t M Alla n J Clark H mesta k Mi ning Co

1 o r . .
, o e .
1 58 A M A N UAL OF F I RE A S S A YI N G

me a ns of a sp a tul a to a gl a zed p a per a n remove a ny a dhering

"

, d
lith a rge fro m the dish by me a ns of a moist piece of fil t er-p a per ,

th o roughly wiping out th e dish If the ev a pora tion h a s not b een .

c a rried t oo fa r this ca n re a dily be done Then mix in a 20 gra ms .

crucible 25 gr a ms lith a rge 1 5 g ra ms N a , CO, 2 gr a ms a rgol 2

d d
, , , ,

gra ms S iO2 a n 5 gra ms bor a x gl a ss a n tr a nsfer the lith a rge fro m

d d
,

the ev a por a ti o n a n fil t er p a per to the crucible a n a g a in mix

d
-

d
d
with a sp a tul a F use the ch a rge a n proc eed a s usu al Unl ess
. .

silver is t o be determined a silver fo il to the crucible before

fusion .

E v a por a ti o n meth o ds conducted in dishes m a de of l ea d f oil

h a ve the dis a dv a nt a ge o f permitting the use of c o mp a r a tivel y
sm a ll qu a ntities of so luti o n onl y a n very frequently give lo w d
results .

T HE A S SAY OF S LA G S A ND CUP E LS FOR T HE CO R R E CTION

A SS AY — S l s The ch rge these depends u p n wheth r
( )
a
. ag : a f o r o e

th ey a r e a cid o r b a sic P a rticul a r c a re must b e t a ken to get a

.

ch a rge th a t will compl et ely dec o mpose the o rigin al sl a g If thi s .

is a cid the ch a rge sh o uld ai m to m a ke a new sl a g more b a sic

d
, ,

d
The le a d button should be from 25 to 30 gr a ms
d d
an vi ce ver sa .

in weight Ma ny a ss a yers frequently a

. simply lith a rge a n
reducing a gent t o the sl a g in m a king the fusi o n This is not .

a lw a ys d esir a ble f o r if t h e sl a g a lre a dy h a s much lith a rge in it

, ,

sod a etc m a y With profit be a dded as the extr a b a se in pl a ce

,
.
,

o f lith a rge .

( )
b C upels The b ne h f the cupel will not unite with
d
: -
o a s o

fluxes to form sl a gs but rem a ins suspend e in the fusion F or

,
.

this re a son the cup el sh o uld be put thro u g h a 1 50 to 200 mesh -

screen b efore a ss a ying the lith a rge st a ined p o rti o n o nl y being

,
-

t a ken Fo r one l a rge cupel or t w o sm a ll ones t h e ch a r ge is a s

.
, ,

follows
Cup el
Pb O 60 g ra m s
Na z O
C 2 5 gr a ms

Fluorsp a r is not d esira ble in the a ss a y of cup els a s it merely ,

a dds a noth er ingredient in suspensi o n

d
.

Ma gnesi a cupels m a y b e flu x e with the f ollowing ch a rge

Cup el B ora x gla ss 20 gr a ms
Pb O 4 0 gr a m s S i lica 10 g r a ms

Na C,
2 5 gr a ms
B or a x c o ver
 S PE C A I L M ET H OD S OF ASSAY 1 59

Cement cupels a r e m o re e a sily flu x e a n a n ordin a ry crucible dd

c h a rge for a som ewh a t b a sic o r e will a nswer v ery well .

T HE A SSAY OF MATE R IA L CONTAINING M E TALLI C IR ON 1

.

Ma ter i a l of this kind will be obt a ined in the cle a n up of mort a r

b o x es of st a m p mills the i ron being present a s pell ets a n much
, ,
d
l a rger pieces mi x ed with s a nd pebbl es etc It c a nnot be crushed
d
.
, ,

an is a ss a yed in the st a te received It s correct s a mpling is .

pr a ctic a lly impossible Cr u cible fu sions a r e m a de in the pres

d
o

ence of bisulp h a te of sod a a n ni ter The ch a rge is a s foll o ws .

Ma t er ia l t o b e a ssa yed 1 a ssa y ton

Bisu lp ha te of so da 8 t o 24 g r a ms
Na , CO, 25 r a ms g
S i0 , . 10 gra ms
25 gra ms
35 gr a m s
1 to 4 gr a ms

d
The fusion should be conducted a t a high h ea t fo r a bout 4 5
d
t o the crucibl e 1 5 gr a ms o f Pb O mixed with
d
minutes Then a .

2 gra ms a rgol a n continue fusi o n fo r 20 min more until quiet . .

The a ction of the bisulph a te is prob a bly a s follows It bre a ks .

up on he a ting .

2 Na HS O, N a , S O4 H, O S O,
The met all ic iron is converted into FeS O4 by the S O3 in the e a rly
d
d
st a ge o f the fusion a n is then c o nverted into ferro us silic a te a s the
d
,

t emper a ture rises The lith a rge a n niter a i in the o xid a tion of
.

the iron Pr a ctic a lly a ll o f the Pb O is reduc ed by the met a ll i c

d
.

iron Inter a ction a lso t a kes pl a ce between t h e N aHS O, a n the

.

N a , COs dependent on the qu a ntities p resent N a , CO, m a y with .

a dv a nt a ge be repl a ced by lime fo r this re a s o n The ch a rge m a y .

h a ve to be modified consider a bly in qu a ntities of the rea gents

present to suit the m a teri al to lie a ss a yed .

1 “
d
Mo ifica tion of Meth o dHof . R . J lly
o ,
”
J o u r Ch em M et
. . a n dM i n S oc S A
. . . .
. VIII .

3 43 .
 CH A PT E R XI

E R R OR S IN T HE AS S A Y FOR G OLD A N D S I LV E R

LOSS E S IN T HE CUPE LLA TION OF PUR E G OLD AND SI LV E R .

These losses m a y be divided into ( 1 ) losses by a bsorption (2) losses

d
,

by vol a tiliz a ti o n The losses of gold a n silver in the cupell a ti on

.

a r e functi o ns of (a ) th e tem p er a ture of cu p ell a tion ; (b) the a mou nt

of le a d with which the gold a n silver is cupelled ; (c) t h e physic a l d

d
n a ture of the cupel ; ( ) the n a ture a n a mount of impurities d
present ; (e) the influence whi ch silver h a s on the gold lo ss a n ,
d
vi ce ver sa .

There is consider a ble liter a ture ext a nt upon l o sses in cupell a

tion of the two preci o us m et a ls but in t h e older rese a rches the ,

d
tempera ture influence is but v a guely defined owing to the l a ck ,

of me a ns for re a dy a n s a tisf a ct o ry temper a ture me a surements ,

a deficiency which is now suppli ed by the LeCh a t el ier pl a tinum

rhodium pyrometer Losses a r e a lso express ed a s percent a ges of

d
.

the tot a l a mount o f met al cup elled a n then th e a ver a ge per ,

c ent a ge losses a r e indic a ted Th a t this is very deceptive is m a de

.

evident by reference to the curve of l osses a ccom p a nying this

ch a pter .

d
It is for this re a son th a t the st a tement of results g iven by
Ma s o n a n Bowm a n th a t the a ver a ge loss in cupell a tion of pure
d
1
,

silver und er n o rm al conditions 1 8

d
p er cent a n for gold .

per cent d o es not convey a ny v ery efinite ide a u nl ess the

.
, ,

a mount of met al cupelled is a ccur a t ely specifi ed a s well a s t h e ,

”
tempera ture This f a ct h a s been noted by other o bs ervers but
.
,

no e ff o rt h a s b een m a de to express results coordin a tely .

The following d a t a show the losses which occur

1 J o ur A m Ch em S oc , XVI
d
. 50 5

d
. . . . .

K fa u m a n, i n E ng a n M i n J o ur
. . .
. LXXIII , 829 . Miller an Fulto n, in S chool f
o

M i nes XVII , 1 69
1 62 A MA N UAL OF F I R E A S S A YI N G
—
TAB LE XXX C . UPE LLATI O N OF P UR E S I LVE R .

( KA U F MA N 1
)

d
P a rentheses indic a te di fferent types of cup els viz bone h ,
.
,
-a s

m a de up respectively with p ea rl ash a n st a l e beer The m a in

- .

figures were o bt a ined by b o ne ash cup els m a de up with w a ter - .

The resul ts vi ewed a s a whol e indic a t e th a t a ll three types h a ve

, ,

equ a l merit G odsh a ll (T a ble XX I X)

. e x perimented with ,

di ff erent types of st a nd a rd b o ne ash cupels (s o me m a de a t t h e

-

mint) with the s a me result

, .

The a greem ent a mongst the di ff erent writers i s v ery cl o se ,

wh en the f a ct is t a ken into c o nsid er a tion th a t in t h e l a st t w o

c a ses no precise st a tement c o ncerning t emper a ture is m a de a n ,
d
th a t t h e a m o unts of le a d di ff er somewh a t .

E a ger an d
W el c h .

G o d sha ll
Ka ufm a n
Liddell ’
.

1 E ng . a d
M
n i n J o ur
. .
. Lx x m 526
, .
{
d
El m a n M i n . J a mi ,m , 1 26 4 .
E RR O RS IN T HE AS S AY F OR G OLD I VE R
A ND S L

ssoq I o m
g s-ze
.

d
 A M A N UA L OF F I RE AS S AYI N G

The a ccomp a nying curves a re constr ucted from fi g ures in Mr

d d
.

G o sh a ll s p a per The gener a l a ver a ges a re t a ken a n whil e

’
.
,

d
his l o sses a r e per h a ps a t r ifle higher th a n the best work c a lls
fo r a t the present a y (o wing t o a better rec o gni tion of the precise
temper a ture required) they form the best a n most c o mplete , d
d
d a t a for the construction of curves sh o wing the rel a tion between
a mounts of sil ver cupelled a n the percent a ge l o ss I refr a in .

d
fro m a m a them a tic a l discussion but a n equ a tion covering the ,

c a se is tent a tively oflere

’
1
.

d
The influence of the size of le a d butto n is cl ea rly disc ernible
by the or in a te s of the curve s The tem p era ture v a ri a tions will .

show in the s a m e w a y .

The liter a ture o f gold lo sses i s consider a bly less th a n th a t for

silver R o se discusses them in the gold bul lion ass a y
.
2
He .

g ives the tot a l lo ss o n b ul li o n fine under n o rm a l tempe r a ,

ture conditi o ns a s fro m per 1 000 o f which 8 2 per cent

d
,
to , .

is cupel a bso rpti o n 1 0 per cent v ol a tiliz a ti o n (prob a bly) a n

,
.
,

8 per cent s oluti o n in a cid

. This c a lcul a ted t o percent a ge on
.
,

a ctu al g old is eq ui v al ent to

,
per cent fo r the high est loss . .

d
( This is cupel loss o nl y not including s o luti o,
n l o ss ) .

d
H ill ebr a nd a n Al len s resul ts cont a in interesting d a t a re
’

g a rding t h e rel a tive l o sses by a bs o rption a n vol a tiliz a tion t o ,

which reference will be m a de a g a in .

CUP LLATIO N G OL D S ILV R A LL OYS — The l o ss Of gold

d
E O F - E
silver in cupell a ti o n is somewha t di ff erent when both gold
d
an

an silver a r e present from the loss when either met a l a lone

is present .

TA BLE XXXI .
— CUPE LLA T ON OF G OLD
( E A G ER A ND WE LCH )
”

I dd
m in eb te to Pr 0 f C C V a n uys, M A N d
d
1 a . . . .
. for th e cur ves a n th e equ a ti ons .

M eta llur g y o f ol G
1 902 , p 506
d
1 .
, .

“
s
N A y ”
p
d
Lo g e, o tes o n ssa ing , . 1 42 .

Ofa ir in m u s. m
irec tly a bo ve cu pel .
 A MA N UA L OF F I RE AS S A YI N G
—
TA BLE XXX I V C . UPE LLATI O N OF G O L D-S I LVE R ALL OYS
( H I L L E R R A N D A N D ALLE N )

ALL CU PE LLA TI ON S M A D E W I TH 25 G R A M S or LE A D
T o ta l lo ss V z
o la tili e d
Am Am
d
o u nt o unt

g ol S i l ver T emp .
0
0 .

S il ver Gol d S il v er
p er p er p er
c ent. c ent . cent .

7 50 ( a ir in m uffl e)
d
°

increa se

R o se sho ws (T a ble XXX III) the p r o tective a ction th a t sil ver

d
exercises over gold the tot al l o ss of gold decre a sing as the a mount
,

of silver present incre a ses H ill ebr a nd a n Al len S h o w how the

d
.

tot a l loss is distributed between a bsorpti o n by the cupel a n

v ol a tiliz a tion It is evident th a t while the tot a l l o ss of gold is
.

decre a sed by the presence of silver the vol a tiliz a tion l o ss of gold
d
,

is incre a sed by t h e presenc e of silv er (c o mp a re T a bl es XXX II a n

XXX IV) Wh en gold a n silv er a r e present in th e r a tio of 1 t o
. d
2 the a ver a ges a r e a s foll o ws
,

Of the tot a l gold l o ss 6 8 per cent is a bso rbed 3 2 per cent is

,
.
,
.

v ol a tilized .

Of the tot a l silver l o ss 7 1 per c ent is a bs o rbed 29 per cen t,

.
,
.

is v ol a tilized .

H o wever a s t h e t o t al l o ss is determ ined by the diff erence in

d d
,

weight between the proo f gold a n silv er a n the w eights o f t h e

d d
.

cupelled b ea d a n p a rted gold a n the v ol a tiliz a ti o n item by

d d
,

the ifier ence between the to t a l loss a n the a m o unt recover ed

by the r e a ss a y of the cup el it is evident th a t ce r t a in erro rs ob t a in
-
,
.

which a pp a rently m a ke the v ol a tili za tion loss a ppe a r gre a t er

 E RR O RS IN T HE ASSAY F OR G O L D A ND S I LVE R 1 67

th a n it re a lly is The e r ro r h o w ever c a nnot be very gre a t

.
, ,
.

d
The d a t a a r e inc o nclusive reg a rding the influence of the tempe r a
ture on the rel a tive losses by a bso rpti o n a n vol a til iz a tion b u t ,

it seems indic a ted th a t the vol a tiliza ti o n l o ss is pro p o rti o n a tely

gre a ter with a n incre a se of t h e tempera ture of cupell ation .

LOSS E S I N T HE A SS AY OF O S — T a bl e XXX V et c show

d d
R E .
,
.

losses of gold a n silver in t h e a ss a y o f o res during fusi o n a n ,

cup ell ati o n a s influenc ed by the pres ence o f cert a in im p uri ti es

,
.

TA BLE XXXV .
— TE LL UR I DE O R E S

Am o unt gold in w eight

of Weigh t of

o f o re t a ken f o r a ssa y lea d butt on

Mi l l i g r a m s G ra ms

1 W d
oo w d in W t Ch m
ar , nd M t I 12 es . e . a e .
, , .

“
F l t n in S h l f M i n Q t X IX 4 1 9
L d
1
u o , c oo o es ua r .
, , .

in T h Q 1 8 9 9 X II 1 7 1 (
dd
"
1 o g e, t ec . ua r
g .
, , a v er a es ) .

B ll NO 2 53 U S G S y( ; Hill b A
Of 34 f i n t llu i m in ll b d
1
u . .
, g . . . ur v e a v er a es e ran an l len) .

1 A v er a
g e us o s, e r u a ea s.
1 A v er ag e of 10 fusions .

7 Cripple Creek flux .

11 E
x
cess-li th ar g e ch a rg e .
 A M A N UA L OF F I R E AS S A YI N G

TA BLE XXXVI .
— Z I NCIFE R O US MATE R I A L , ET C .

A mo u nt Of A
d
u

W ig h t
d
an Ag in e

w eig h t of or e of lea S la g loss

ta ken for as b u t to n

Meth o d o f a ssa y R e mar ks

Au Ac AU AC
G ra ms p er p er p er p er
cent . ce nt. c ent . cent .

S cor ifica tio n f

d
28 7 0 a te r 0 06 0 0 11 1 30 Z n p p t . . co nta ini ng

ac i tr ea t ment p er cent. Zn
f p
d
23 2 0. fi
S co ri ca tio n a te r 0 04 Fig ur es r e r esent

aci tr ea t m ent a v er ag es .

28 4 0 D ir ec t cr ucible 1 04 1 0 16 1 50
f usio n

Crucible fusi o n
d
1 97 0 0 06 0 51 0 Zn .
p p t containing
.

a f ter aci tr ea t p er cent . Z n,

ment p er cent. Cu .

202 0 Di r ec t c r u cib le 0 16 1 Fig ur es re present

fusion a v er ag es

f G
d
56 1 0 Cr u cib le usio n 38 a lena

nite r meth o
Cr ucible f usio n G
d
56 7 0 42 a lena

nite r meth o
Cr u ci b le f usio n
d
1 75 0 90 S ilicio us ore co n

ni ter meth o t a ining so me c opper

1 74 0 20 1 66 S ilicio us ore co n

ta ining so me
00 9 9 9 ?

F d d Q XX II
d
1 ul t on a n C ra wf or , in S cho ol f M i nes
o ua r t .
, , 1 53
1 Lo g e , in T ra ns . A I
. . M E
. XXXI V 4 3 2
.
, , .

1 Miller in S ch ool
, o f M i nes Q t X IX 4 3
ua r .
, ,
1 70 A M A N UA L OF F I R E A S S A YI N G

to be a scrib ed to the n a ture of t h e m a teri a l ass a yed chiefly t o ,

the influence o f cert a in elem ents p resent In c o nsid ering t h e . .

p ercent a ge Of loss it mu st be rec a lled th a t this v a ries invers ely

,

with the a m o unt of preciou s met a l in the ch a rge i s with t h e , . .

,

size of the go ld silver be a d The sum Of the cupel a b so rpti o n

d
- .

an the sl a g loss (which ca n in p a rt b e recovered) is not t h e , , ,

tot a l l o ss a s it does not include th a t by v ol a tiliz a tio n which is

, ,

sm a ll in m o st c a ses but in some c a ses a g a in m a y be quite a ppre

, , ,

cia ble a s in the c a se o f tellurid e ores

,
Wh a t the los s is in sl a g .
,

when no element like tellurium copp er zinc etc is present ma y , , ,

.
, ,

b e seen by reference to T a ble XXX V I to tho se a ss a ys fused a ft er

d
,

a cid tre a tment a n t o T a bl e XXX V I I showing crucible f u si o ns on

d
, ,

d
le a d c a rbon a te o r e The sl a g loss in gold a n silver for these o re s
.

is very sm a ll In c ases where the i mpurity present a n c a using

.

d
loss is ne a rly all elimin a ted in the fusion e g zin c a ntimony ,
. .
, , ,

etc the cupel a bsorption is pra ctic a lly th a t for pure silver a n
.
,

gold under the sa me circumst a nces Where the impu rity is .

tellu rium or selenium or copper the cupel a bsorpti o n is decidedly

, , ,

incre a sed One f a ct is t o be no ted the f a ct th a t the sl a g losse s

.
,

present no regul a rity even for the s a me m a teri a l This is prob

,
.

a bly due p a rtly t o di ff erences of sl a g c o mpo sition a m o ng

d
diff erent exp erimenters a n p a rtly to di ff erence of temper a ture
d
,

of fusion ; a n a lso to the m eth o d of refusi o n of sl a g .

The high loss in scorifica tio n sl a gs shown in T a bl e XXX V II fo r

le a d c a rbon a te ores cont a ining silver is due to the genera l u n
suit a bility o f the o re fo r sco rific a t ion a lthough sco r ific a t io n ,

sl a gs show higher l o sses th a n c r ucible sl a gs Th a t in spite of .

,

this scor ifica tio n a ss a ys o n silver be a ring m a teri a l S h o w equ a lly

d
-
, ,

good a n better results in m a ny c a ses th a n the crucible a ss a y is ,

due to the f a ct th a t the silver be a ds ret a in sm a ll qu a ntities Of

d
le a d a n copper (see further o n) a n to the f a ct th a t in the multi ,
d
plic a tion of the weight of the silver be a d by 5 o r 1 0 or wh a tever ,

the a ss a y t o n f a ct or m a y be this erro r is multiplied giving a n

-
, ,

a pp a rently better result .

The a m o unt of sl a g h a s comp a r a tively little influence on the

a mount Of preci o us met a ls ret a in ed p ro vid ed the a mount of ,

c oll ecting l ea d is a mple Butt o ns of less th a n 1 8 t o 20 g ra ms

d
.

sh o uld no t be m a de if the a mount o f sl a g is gre a t o r t h e

d
an ,

qu a ntity of silver a n gold in the ch a rge is m o re th a n 500 mgs

d
,
.

25 a n 3 0 gra m buttons a re essenti a l

- In the c a se Of l a rge .

butt o ns which cont a i n no impurity it is a l so b est t o cup el direct , ,

 RR O RS G O LD I LV E R
g

E IN T HE A SSA Y F OR A ND S 111

if po ssibl e r a ther th a n resco rify to sm al l er siz e a s t h e r esco rifi

, ,

c a ti o n c a uses gre a ter l o ss th a n the direct cupell a ti o ns .

D uring sco rific a tion th ere is a l so a n a ppreci a bl e l o ss o f the

precious met al s by v ol a tili z a ti o n which is a bsent in the crucible ,

a ss a y Thi s in t h e c a se o f tell uride or zincifero us ores m a y

.
, ,

b ecome S O gre a t a s t o put scorifica tio n out o f the questi o n

d dd
.

OTHE R E R R OR S — R etenti on of Lea i n Cu pelle Bea s — S m al l

qu a ntities of le a d a r e a lmost inv a ri a bly ret a ined in the gold a n d
silver b ea ds with ordin a ry temper a tures o f cupell a tion H ill e
d
.

bra nd a n Al len in t w o c a reful exp eriments on s ets o f three

1
,

b ea ds a pproxim a tely t o gether 90 mgs gold found th a t

d
, p e r .
,

cent a n . per cent respectively of l ea d were ret a in ed .

, ,
.

This retention of le a d c a nnot be c o rrected by le a ving the be a d

in the mu ffle for some l en g th of time a fter the blick a s this is of
d
, ,

c o urse prohibitive in the c a se of silver a n in the c a se o f gold

, ,

see m s to a ctu al ly c a use a n incre a se of weight It h a s a lrea dy

d
.

b een st a ted th a t c o pper a n tellurium a re very a p t to be present

in t h e fin a l be a d when in t h e o r e in a ny a ppreci a ble qu a ntity
,
.

The retentio n of b a se met a l by t h e be a d c a uses a plus e r ro r in

silver but will not efiect the resul t on gold u nl ess the p a rting is
d
,

by H, S O, ; a n where the weight of the be a d is mul tiplied by a

f a ctor to g et results per ton the fin al error in silver m a y be v ery ,

a ppreci a ble The presenc e of copp er in t h e fin a l be a d pra ctic a lly

.

insures t h e complete rem o v a l of the le a d .

In order to show wh a t is usu a ll y termed fine silver the fo llow

ing a n a lysis of G overn m ent fine silver is a pp ended .

Ag , Cu Pb Au ,
As , , ,

d
Sb Fe Z n t r a ce 2

dd
, , ,
.

R etenti on of S ilver by the P a r te G ol — Ordin a ry p a r te go ld

d
,

a ft er the pr o per tre a tment with we a k a n stro ng a cid ret a ins ,

fr om to per cent of silver In the a ss a y of gold bulli o n . .

a fter the first a cid tre a tment of the qu a r t a ti o n a ll o y the g o ld ,

on the a vera ge ret a ins per cent silver A fter the sec o nd . .

a cid tre a tment the fin a l silv er retenti o n is fro m

, to
p er cent d epending on t h e time of b o iling If t h e a m o unt of
.
, .

silver to gold in the qu a rt a tion a ll o y is less th a n t o 1 so me ,

wh a t m o re th a n the a bove a m o unt of silver will b e ret a ined 3

.

S ilver c a n pr a ctic a lly be completely extr a cted by m o re th a n

, ,

1 B ul l NO 253 , U S G y
dXV
. . . . . S u r ve .

1 M in In ,
dp
.
, 54 5 . .

“
3 R o se, M eta llur g y o f G ol , . 4 53 .
1 72 A M A N UA L OF F I R E A S S A YI N G

two tre a tments with a cids a cc o rding t o H illebr a nd a n A ll en ,

d .
1

d
In the ordin a ry a ss a y for ores a s usu a lly c a rried o ut it is s a fe t o ,

a ssume th a t some sil ver is inv a ri a bly ret a ined b y the gold a n ,

frequentl y much more th a n is supp osed ; however with lo w ,

r de ores this retention i negligible

d d
g a s , .

S olution of G ol by A ci — I t is es senti a l th a t the nitric a cid

dd
used for p a rting be free from impurities especi a lly from hydro ,

d
c hlo r ic a ci an chl orine ; otherwise soluti o n o f gold is sure t o
follow G old is quite soluble in mi x tures o f h o t sul phuric a n
d
.

“
d
nitric a cid a n is a g a in precipit a ted by dil uti o n
d
.
,

A ccording to H illebr a nd a n Al l en ni trous a cid (HNO, ) a n

”

d d
,

mixtures of HNO3 a n HNO2 o not diss olve gold though there ,

is much e a rlier l i ter a ture to the contr a ry N itrous a cid h a s .

frequently been consid ered i n th is connection a s it is formed t o ,

some extent by the a ction Of HNO, o n silver .

A ccording t o R o se ‘
some gold is dissolved by nitric a cid on ,

continued b o iling t o const a nt gr a vity of a cid This solutio n is .

d
pl a ced in the bullion a ss a y a t per cent or p a r ts per 1 000 ‘

. .

H illebra nd a n All en st a te th a t the loss Of gold by solution is

d
very sm a ll a n irreg ul a r It m a y be disreg a rded in the ore a ss a y . .

The solubility of gold in HNO, is re a d ily dem o nstr a ted when l a rge
qu a ntities Of gold a r e used F P D ewey in c a reful experiments
5
. . .

showed the solution o f gold to the extent of 66 0 mgs per liter of .

o f conc a cid on boiling a bout 25 gr a ms gold fo r t w o hours

.
,
He .

st a tes th a t the temper a ture ( 120 C ) required t o b oil co nc a cid

°
. .

h a s a s decid ed a n influenc e a s the strength of the a cid

d
d d
.

Occlu e G a ses P a r ted gold be a ds a n

— c o rnets ret a in
.

a bout twi ce their v o lume in occlud ed g a ses a fter a nne a ling The .

princ ip a l g a s is st a ted to be c a rbon mono xide T w o volum es .

a m o unt to per cent by weight which is a lrea dy a llowed for .

,

in the silver retention .

E rr or s i n Weig hi ng — The best sc a les a re a ccura te to mg

d
,
.

an sc a les ca n be o bt a ined weighing to mg This l a st is .

used in a ss a y o ffices where gre a t a ccur a cy is required on , ,

such m a teri a l a s bullions rich m a ttes etc It is usu a lly a n , ,

.

unnecess a ry refinement in the o rdin a ry ore a ss a y fo r the re a son ,

th a t the prob a ble error in the a ss a y is gre a ter th a n this .

1 B ull 2 5 3 , U S
. S ur v e . . G . y .

2
Le nh ar , in J o u r A m Ch em. S oc XXVI
d
. . .
, , 5 52
3

dp
Ibi .

I bi .
, . 507 .

5
J o u r A m Ch em S oc
. . . .
, XXXII , 3 18 .
 CH A PTE R X II
T HE A S SA Y OF BU LLI ON

G N R AL
E E — Bullion is cl a ssified a s follows

d
1 Le a d bulli o n usu a lly the pro duct of the le a d bl ast furn a c e ;
.
,
-

9 5 per cent a n more le a d c o nt a ini n g some copper a ntim o ny

d
.
, , ,

etc silv er a n gold

.
,
.

2 B a se bullion cont a ining from 1 00 t o 9 25 p a r ts o f sil ver

d
,
.

per 1 000 gold in v a rying a m o unts a n a l a rge p ercent a ge of

, ,

b a se met a ls chiefly co pper zinc l ea d etc Produced most

, , , ,
.

frequently by cy a ni de mills .

3 D or! bullion c o nt a ining 9 25 t o 9 90 p a rts o f silver p er

d
.
,

1 000 so me go ld a n b a se met a ls mostly c o pp er but a lso l ea d

, , , , ,

d
a ntimony zinc et c , ,
.

4 Fine silver bulli o n f r ee fro m go ld c o nt a ining 99 0 a n more

.
, ,

p a rts silver per 1 000 but so me b a se met a ls usu a lly c o pp er

d
.
, ,

5 S ilver bulli o n c o nt a ining little b a se met a l a n less th a n

.
,

d
h a lf its weight in gold .

6 G o ld b ul li o n c o nt a i ni ng little b a se m et al a n more th a n
.
,

h a lf its weight in gold .

7 F ine go ld bulli o n free fro m silver c o nt a ining fro m 9 9 0 t o

.
, , ,

1 000 p a rt s gold per 1 000

d
.

S ilver a n go ld in a ll bulli o ns but l ea d bulli o n a r e estim a ted

in p a rts per th o us a nd a n bul li o n is s a id t o be so m a ny p a rt s
,
d
fine Thus if 1 gr a m ( 1 000 mgs ) of bulli o n is t a ken fo r a ss a y
d
.
.
,

an it c o nt a ins 9 25 mgs gold it is s a id t o b e 9 25 fine .

,
.

“
d
In the a ss a y Of gold bul li o n the millieme system o f a ss a y
weights is us ed a milli eme being 0 5 m g a n the a ss a y is r e
,
. .
,

p o rted in p a rts o f o r t h e fin eness with o ne decim a l a dd ed .

Thus the a b o v e bulli o n w o uld be rep o rted a s fine In .

this system t h e 500 m g w eight is st a mp ed 1 000 t h e 250 m g

- .
,
- .

w eight 500 etc T h e sc a l es used must th erefo re b e sensitive

,
.

to mg or .milliem e This p r esents no di fficulty a s

,
.
,

o rdin a r y a ss a y b a l a nc es a r e s ensitive to mg with a l o a d of .

gr a m .

Lea d bulli o n is rec o rd ed in o z p er t o n in t h e s a me w a y a s .

,

for ores .
 T HE AS S A Y OF B U L L I ON 1 75

U
The sa mple of bul l i on ma y
d
T HE A SS AY OF L A D B LLION
E — .

be melted under ch a rco a l a n gr a nul a ted in cold w a ter o r it m a y

d
,

be rolled out into a strip in the rolls a n the pieces cut a t inter ,

v al s from this fo r the s a mpl e If le a d bullion is free from c o pper

d
. .

a ntimony zinc sul phur a n a rsenic etc it ma y be cupelled

d
, , ,
.
,

directly for gold a n sil ver In this c a se 4 portions of a ss a y

.
,

ton e a ch a r e wr a pped in a b o ut 7 gr a ms of sheet le a d pl a ced in

d
,

the h ot cupels a n cup elled with fe a thers The cupels a re fused

,
.

with the foll o wing ch ar ge

S ta i ned p a r t of cu pel 4 5 g ra msbor a x gla ss

8 0 g r a m s Pb O 2 g r a msa r g ol

15 gra ms Na , CO, Thin lit har ge co ver

The buttons from this fusion a r e cupell ed a n the weight of d

d
the gold a n S ilv er a dd ed to th a t Obt a ined from the first cu pell a
ti o n .

If the bullion c o nt a ins b a se met a ls which will influence the

resul ts of the cup ell a ti o n 4 portions Of either or a ss a y

d
,

t o n a r e w eighed out a n mi x ed with 3 0 to 50 gr a ms of test le a d ;

d
d
gra ms of bor a x gl a ss a n r m f silic put top of
d
g a o a a r e o n
the le a d a n the ch a rge sco rifie The result a nt buttons which .
,

sh o ul d weigh a bout 1 5 gr a ms a r e t hen cupelled The scorifier

d d
.
,

sl a g a n cupel a e e a ss a yed by the a bove ch a rge a n the corr ec

r r -

tion a dded .

T HE A SS AY OF S ILVE R BULLION (a l so a pp lica ble to Ba se Bul

1

li on Dor ! Bull i on
, CUP LLATION
E
,
M E TH O D — This meth o d .

is used a s a n a ppro x im a ti o n for bul lions in which silver is to be

determined a ccur a tely serving a s a prelimin a ry a ss a y for t h e
,

s a lt tit a tio n mint or G a y Luss a c method

r ,
-
,
.

( )
a P r el i mi na r y A ssa y
— E x a ctly 5 0 0 m g s o f bul lion a r e .

weighed out on a n a ss a y b al a nce in o rd er t o s a ve c al cul a tion

d
,

wr a pped in 1 0 gra ms of shee t le a d a n cup elled a t C or ,

.
,

d
with a mpl e fe a thers of lith a rge The S ilver be a d is cle a ned .
,

weighed a n p a rted in 1 to 9 HN O8 fo r a t le a st 20 minutes ; then ,

if a ny gold sh o ws h ea ted fo r 5 minutes mo re in c o ncentra ted

d d
,

a cid w a shed
, an ,
the g old dried a nne a led a n weighed The ,
.

a mount of gold found subt r a cted fro m the w eight Of the b ea d

d
, ,

gives t h e a ppro x im a te silver a n the weight of t h e be a d sub , ,

tr a cted fro m the a m o unt o f bulli o n t a ken (500 giv es the

1 For sa m Of
m i ng sil v er b ullio n, see T he A y ssa of G ol d B ullion, la ter in this Ch a p ter .
 A A N UA L F I R E A S S A YI N G
’

M OF

b a se m et a l This b a se met al is usu all y copper a n its p resenc e

.
,
d
ma y b e d etected by the c oloring of the cupel
d
.

(b) M a ki ng the Check A ssa y A s the l o ss of silver a n gold

—

d
is a questi o n of tempera ture a m o unt of precious met al present
d
, ,

a m o unt o f le a d of cupell a tion an a m o unt a n kind Of b a se,

met al present it is desir a ble to h a ve the regul a r cupell a ti o n

, ,

a cc o mp a nied by a ch eck a ss a y m a de up a s ne a rly a s p o ssible to

d
,

the c o mp o siti o n Of the b ulli o n t o be a ss a yed a n cupelled under ,

the s a me c o nd itions The check a ss a y is therefo re m a de up fro m

.

d a t a o bt a ined in the prelimin a ry a ss a y A s the silver d etermined

d
.

in this prelimin a ry a ss a y is low due to a b so rption a n vol a tiliz a ,

tion a c o rrecti o n Of
, per cent is a dded a s a n a ppro xim a ti o n .

d
or, r a ther the a mount o f A g found is consid ered a s
, per
cent o f th a t present a n thi s a mount of proof silver w eighed
.
,

o ut . To this is a dded in pro o f gold the a m ou nt of gold fo und

, ,

in the prelimin a ry a ss a y The di ff erence between the sum of

d d
.

the c o rrected silver a n t h e gold a n 500 is the a mount o f b a se , ,

met a l t o be weighed o u t for the check

d
A s a lrea dy st a ted the .
,

b a se met a l is usu a lly c o pp er a n in m a king up the check c p

d
. .
,

sheet c o pper is used The check thus weighs 500 mgs a n a pprox
. .

im a tes very clos ely the c o mp o siti o n o f the bull ion D uplic a tes
d d
.

o f 5 00 mgs of bulli o n a r e no w w eighed out a n

. thes e a n t h e ,

check e a ch wra pped in t h e pro per a mount of sheet le a d a s de

d
,

t er mine fro m the t a bl e below

TA BLE XXX I X .
— L E AD R ATIO I N C UPE LLATIO N

R a t io Of lea d
to ba se m eta l
G ra m s

() c T he A ssa y — Three cupels a r e pl a c ed in a row a cross the

mu ffle so , as to be exposed a s ne a rly a s p o ssible to the s a me
1 78 A M A N UA L OF F I RE AS S A YI N G

by t a king 1 p a rt of the st a nd a rd Na Cl solution a n a dding to it d

9 p a rts of distill ed w a ter) a n a n a cidul a ted solution of A g NO, , d ,

Obt a ined by disso lving 1 gra m o f proof silver in 1 5 c c of HN O,

d
. .
,

sp g r a n .diluting .with
,
disti lled w a ter to 1 000 c c I t . .

foll ows fro m the a bo ve th a t 1 c c of the one tenth solution will

- . .

j ust preci p it a te the A g in 1 c c of the a cid ul a ted silver nitr a te . .

solution .

“
The st a nd a rd Na Cl soluti o n is ter med the norm a l sa lt

d
s olution in the ass a y a lthough not properly so ; the we a k solutio n
,
“ ”
is termed the decim a l s a lt solution an the sil ver nitra te ,
“
soluti o n the decim al silver solutio n
dd
.

S ta n a i zi ng S oluti ons
r — The a pp a ra tu s requi r ed is .

1 A l a rge b o ttle o r c a rboy cont a ining the n o rm a l s al t solution

.
,

pl a ced on a n elev a ted shelf so th a t the solution m a y be si

p honed by me a ns of gl a ss tubing a n rubber h o se to the m a in d
1 00 c c pipette
d
- . . .

2 Liter bottles cont a ining r espectively the decim al s a lt a n

.

the decim a l silver so luti o ns .

d
3 A n a ccur a te 1 00 c c pipette cl a mped to a suit a ble st a nd
.
- . .
, ,

an p rovided a t the top with a gl a ss o v er flo w cup cont a ining a -

m o istened sponge t o c a tch the overflow of t h e no rm a l s a l t

solution .

d
4 T w o sm a ll g r a du a ted 1 0 c c pipettes o ne for the decim al
.
- . .
,

sa l t a n one fo r the decim a l silver soluti o n Burettes ma y b e .

used i n pl a ce of these .

d
5 A numb er Of stro ng 8 t o 1 2 o z bottles simil ar to re a gent
.
- .
,

bottles pro vided with r b b er c o rks

,
.

The st a nd a rdizing of so luti o ns is c a rried out a s follows : T w o

p ortions of ex a ctly 1 002 mgs pro o f silver a r e dissolved in 1 5 c c . . .

Of sp g r HNO the nitrous fumes a r e rem o ved by b o iling

d
.
S
.
, ,

the soluti o n is tr a nsferred to the titr a ti o n b o ttles a n w a ter

a dd ed t o bring up the a m o unt o f solution t o 1 25 c c The 1 00 c c
- . . . .

pipette is then fil led with no rm a l s a lt solution t o the m a rk a fter

.
,

w a shing o u t with s al t solutio n t o p revent dilutio n The filling .

is done by f a stening the siphon hose t o the bottom of the pi p ette

d
,

opening the cl a mp on the hose a n l etting the pipette fill with a , ,

littl e overflow The solution is then shut 0 3 by cl a mping the

.

hose a finger pl a ced on the top o p eni ng o f the pipett e t o prevent

d
,

d
the solutio n running out a n the hose removed The pipette ,
.

is then p er mi tted to dra in to the 1 00 c c m a rk a n the solutio n

- . .
,

h eld t here b y clo sing th e top of th e p i p et te wi t h th e fi ng er T he .

 T HE A S S A Y OF B U LL I ON 179

d
bottl e c o nt a i ning the dissolved proof silver is then pl a ced under
the pipette a n the norm a l s a lt soluti o n permi tted to complet ely
dr a in into it The bottle is then Violently sh a ken fo r three or
d
.

four minutes either by h a nd or a m ech a nic al a git a tor a n the

, ,

A g Cl a llowed t o settle l ea ving the supern a t a nt liquid cl ea r

,
If .

t h e no r m al soluti o n is m a de up c o r rectly it will h a ve precipit a ted ,

j ust 1 000 mgs of silver l ea ving 2 m g s unprecipit a ted One c c

.
,
. . . .

Of decim al s a lt soluti o n is no w a dded t o the b o ttle by me a ns o f

one Of the 1 0 c c p ipettes or a burette which if the s olution

- . .
, ,

sti ll cont a ins A g unprecipit a ted gives rise to a white cl o ud of ,

d
A g Cl . The bottle is a ga in sh a ken the preci p it a te all owed t o ,

settle a n ,
a nother c c o f decim a l s al t s o luti o n a dded
. . If this .

f a ils to g ive a precip it a te then c c Of norm a l s a lt solution

,
. .

a r e equiv al ent to 1002 mgs of silver ( 1 c c of d ecim a l s al t soluti o n . . .

c c norm al s a lt so luti o n) If the sec o nd a ddition o f

d
. . .

d
decim al s a lt solution g ives a p recipit a te the sh a king a n settling
d
,

a r e r epe a ted a n a third a n f o urth etc

, a ddition m a de until no ,
.
,

further cloud a ppe a rs The ass a yer s o on l ea rns to j udge by the

.

density Of t h e cl o ud whether b nly p a rt of the c c h a s been used . .

up In this w a y he sho uld be a ble to j udge to the fo urth of a

.

c c or the h a lf of a milliem e
. . If the first a ddition o f decim a l .

sa lt solution f a ils to giv e a precipit a t e the n o rm a l solution con

d
,

d
t a ins a n excess o f s al t a n 2 c c of decim a l silver solution a r e
,
. .

now a ded o ne o f which n eutr a lizes or precipit a tes the 1 c c of

, . .

decim a l s a lt s oluti o n a dded t h e other a cting on the excess of s a l t ,

in the s olution The decim a l silver solutio n is a dd ed until no

.

furt her cl o ud a ppe a rs in the s a me w a y a s de sc ribed for the

,

decim a l s a lt solution In this w a y the ex a ct strength of the

.

norm al s al t soluti o n is determined in duplic a te If it is incorrec t .

t o the ext ent of more th a n 2 p o ints fin en ess either w a y either

stro ng or we a k) it is corrected by the a ddition of either w a ter
d ddd d
,

o r s a lt an ,
r est a n a r iz e an wh en corr ect a new decim al , , ,

s a lt solution m a de up fro m it Its strength is fin a lly recorded .

o n the bottle a s foll o w s : 1 00 c c = 1 000 mgs A g or wh a tever it . . .

,

ma y a ctu a lly be .

T he A ssa y — I t is evident from the preceding th a t the a mount

o f bullion t o be t a ken for a ss a y must c o nt a in a s ne a rly a s p o ssible

d
1 000 mgs A g in order to m a ke the titr a tion with solution a s
.

'

sh o rt a s p ossible an a vo id undue a dditi o ns o f the decim a l

,

solutions F or this re a son the bullion on which the silver deter

.

min a tion is to be m a de is first a ss a yed by the cupell a tion method ,

180 A M A N UA L OF F I R E AS S A YI N G

prelimin a ry a ss a y desc ribed under this meth o d is

l ea st
d
or a t a , ,

m a de a n fro m these d a t a t h e a mount of bulli o n cont a i ning

,

1 000 mgs of silver c a lcul a ted . For inst a nc e supp o se the cupell a .
,

t i o n meth od shows t h e bullion to be 900 fine in silver then ,

900 1 000 1 000 x .

fineness of bullion silver a mta m t of bullion

. . .

mgs bulli on cont a ins 1 000 mgs A g This a mount of

d
or . . .

bulli o n is then weighed o u t in duplic a te a n dissolved in a cid

dd
,
“
pl a ced in titra tion bottles a s described a b o ve under S t a n a r i
d
, ,

z a t io n of S o lutions an titr a ted , .

The c a lcul a tion fo r fineness is a s follows : S upp o se the strength

of the norm a l soluti o n is 1 00 c c 1 00 1 mgs A g a n th a t cc . . .
,
d . .

of n o rm a l solution were used in the titra tion ( 1 00 c c norm a l

d
. .

s a lt a n 2 c c decim a l silv er) ; then

,
. .

1 00 1 00 1

d
a:

the x or a mount of sil ver in b ullion equ a ling

, ,
mgs .
; an

the fineness is

t h e y, fineness equ a ling

or ,

The only m et a l interfering with t h e s a lt titra tion is mercury ,

which will be precipit a ted b y the N a Cl a s n Cl z ; the a dditi o n of

20 c c sodium a cet a te a n a little free a c etic a cid to the a ss a y
. . d
will prevent the precipit a tion of the mercury Mer cury ca n be .

detect ed in the titr a ti o n if the A g Cl h a s not turned d a rk a s the

result o f exposure t o sunlight Mercury will b e fo und sometimes .

d
in mill bull ions which h a ve been reto rt ed a t t o o low a temp er a ture .

The a ss a y a n st a nd a rdiz a tion o f the soluti o n should b e c a rried

out where there is no sun a n where light is not t o o stro ng ,
d .

T HE A SS AY OF G O L D BULLION FOR S ILVER BY A WE T

‘

M THO D
E — The a ccur a te estim a ti o n of silver in bullions cont a in
ing a l a rge pro porti o n of gold is not a ll th a t ca n be desired by t h e
o rdin a ry fire meth o d The G a y Luss a c meth o d is gener a lly .
-

not a pplic a ble on a cc o unt of the l a rge a m o unt of bullion th a t

must be t a ken fo r a s a mple in o rder t o get 1 gra m of silver:
The following wet m eth o d will yield go od results T a ke
1
.

gra m of t h e bulli o n fuse with gm of pure c a dmium under ,

.

a cover Of pot a ssium cy a nide in a porcel a in crucible in the

fl a me of a bl a st l a mp E nough cy a nide must be used t o .

H T a ylor , A M i ni ng S ta n ddA 26 , 1 908 , 23 5 00 t a lso JE

d
1 E . . u str a li a n ar , ug ust . . .

Clennel , E ng . M
an in . J ou r .
, L XXX III , 1 099 .
1 82 A M A N UA L OF F I R E AS S A YI N G

to 1 ofsho uld not be u sed otherwise the co m et Of gold is

'

Au ,

a pt t o bre a k up With less th a n 2 p a rts of A g too much A g

.
,

is ret a ined al tho ugh with continued boiling

,
p a rts A g will
p a rt A u from A g 1
For the prelimin a ry a ss a y 500 mgs ( 1 000
.
, .

milli emes) a r e weighed o u t sil ver a dded a ccording t o j udg ,

5 9 —a nm ns
’
FI O . . R O LLS .

ment to bring the r a tio Of silver to gold t o 2 or (allowing

d
fo r silv er in t h e a ll o y) a n the bul lion a n silver w r a pped in d
d
,

d
1 0 gr a ms sheet le a d a n cup elled a t 8 50 C °
.

The resul t a nt be a d is cle a ned weighed fl a ttened a n rolled , ,

o u t in j eweler s ro lls t o a fil let Of the a ppro xim a te thic kness Of a

’

Visiting c a rd If so me c o pper is present in the bullion eno ugh

.
,

1 R ose, Meta llur g y Of Gol dp

, . 4 93 .
 T HE AS S AY OF B U LL I ON 1 83

is ret a i ned by the gold b ea d t o tough en it a n it ca n be e a sily , d

r oll ed without cr a cking if betwe en reducti o ns by the rolls t h e , , ,

fillet is a nne a led a t a dull red he a t T h e presence of copper

- .

in the button a i ds in the tot a l remov a l of le a d during t h e

d
c up ell a tion
1
.

The fil let is the n a g ain a nne a led a n rolled i nto a spira l

d
,
“
c a lled a co m et a n p a rted in a p a rting fl a sk This is fil led
,
.

with 30 c c of HNO, sp gr free from Cl H, S O H, S O,

d
. . . .
, ,

o r a ny sulphide a n he a ted to boiling (or a t l ea st 9 0 C ) for 20

d
°
.
.
,

minutes The a cid is then dec a nt ed off a n t h e c o m et w ashed

.
,

c a refully sever a l time s with hot distilled w a ter by dec a nt a tion .

d
Then 3 0 c c of boiling nitric a cid sp gr
. . a r e a dded t o t h e ,
. .

fl ask a n the co m et b o il ed a ga in fo r 20 minutes a fter which th e

d
, ,

a cid is dec a nted an the w a shing with h o t w a ter repe a ted

,
.

D uring the boiling a p a rched pea a dd ed to the fl a sk prevents ,

d
bumping The fl a sk is now filled t o the very t o p with cold
.

istilled w a ter a suit a bl y sized p orcel a in p a rting cup pl a ced over

d
-
,

the mouth fitting rea so n a bly tight a n the fl a sk inv erted T h e

d
.
, ,

cornet will settle into the p a rting cup a n the fl ask is then gently
-
,

d
tip p ed to permit the w a ter to esc a pe the w a ter is dec a nted from ,

the p a rting cup a n the co m et gently dried When dry t h e

-
,
.
,

co m et is tr a nsferred to a cl a y a nne a ling cup the cover is p ut

d d
,

on a n, the cup is pl a ced in the mu ffle a n the co m et a nne a led ‘

,

a t a full red he a t -
It is then weighed The weight of the gold . .

plus th a t of the a dded silver subtra cted from the weight of t h e ,

c u p elled be a d g ives the a pproxi m a te a mount of s ilver in t h e

d
,

a ss a y This a dded t o the weight of the gold a n subtra cted

.

from 500 mgs (the weight of bullio n t a ken) g ives th e a ppro xim a te
.

a mount of b a se met a l If the a mount of silver a dded t o p a rt .

the gold h a s r a ised the r a ti o o f A g t o A u over 3 to 1 the gold ,

will prob a bly h a ve broken up or a t le a st p a r ts will h a ve broken ,

from the edges of the co m et ; c a re must in this c a se be t a ken to , ,

collect a ll Of it in the w a shing If the resul ts S how th a t t h e .

ra tio of A g t o A u h a s been l ess th a n 2 to 1 t h e co m et must be

d d
,

r ecu pell e with p a rts A g a n p a rted a s described .

T he A ssa y — The fina l a ss a y is m a de up from d a t a Obt a ined

.

in the prelimin a ry ass a y D uplic a tes on 1 000 milliemes a r e ru n .

,
”
with a Check a ss a y m a de up i n composition a s ne a r to th a t of

d
the bulli o n as possible a s described fo r the cupell a ti o n a ss a y of ,

silver In m a king up the check p roof gold a n proof silver a r e

.
,

R fining G ld
B ul li n in T ns I M M Ap il 13 1 905
”
1 Ro e s , e o o , ra . . . .
, r , .
1 84 A M A N UA L OF F I R E A S S A YI N G

d
used a n c p cop p er foil The U nited S t a tes mints use v a rio u s
,
. . .

proo f a ll o ys in t h e m a king up of check a ss a ys F or t h e a ss a y o f

d
.

fine gold b a rs (990 fineness a n a bo ve) a pro of a ll oy of 1 000

d
,

gold 2000 silver a n 3 0 p a rts co pper is used Fo r coin met a l

, ,
.

( 90 0 p a rts fi ne) a proof a l loy

,
of gold 9 0 0 p a rts S ilver 1 8 0 0 p a rts , ,

d
Copper 1 00 p a rt s is u sed Fo r the determin a tion o f b a se met a l
d
.

( t h e di ff er ence betwe en the gold a n silver a n t h e 5 0 0 mgs ,

.

t a ken for a ss a y) a proo f a ll oy of gold 900 pa rts silver 9 0 p a rts

, , ,

c o p p er 1 0 p a rts is used 1
In this l a st t h e gold need not be proo f
.

gold but m a y be remelted cornets It is t o be n o ted th a t these

,
.

proo f a ll o ys a r e m a d e up on the a ssumpti o n th a t 2 p a rts of A g

to 1 of gold a re used in p a rt ing T h e British mint uses a pro of .

a ll o y o r tri a l pl a te
,
fine in gold ,
.

F or the a ss a y Of crude gold bulli o n i e mill bulli o n the pro o f ,

. .
, ,

a ll o y for fine go ld b a rs is gener a lly us ed .

The a mount o f le a d u sed in the cupell a ti o n is a s f oll o ws : 2

TA BLE XL .
— LE A D R ATIO IN C UPE LLATIO N

1 000 pa rt s
Am o unt Of lea d
R a tio of lea d t o co pper
( b a se m eta l present )
Mi lligr a m s G ra ms

To the duplic a tes of the 1000 milliemes of bullion the proper ,

a m o unt o f A g is a dded t o bring the r a tio of A g t o A n t o 2 to 1

d
, ,

an then th ey a r e wr a pp ed i n t h e prop er a m o unt o f c p sh eet . .

le a d The check is m a de up a s indic a ted by t h e prelimin a ry

d
.

a ss a y a n t h e three a ss a ys cupelled a s described for the a ss a y

d
,

Of silver bulli o n The three be a ds a r e then trea ted a n p a rted

.
,

a s d escribed for the prelimin a ry a ss a y The t w o bulli o n a ss a ys .

should not di ff er by more th a n p a rt o f a milliem e The .

d
d
1 Joh n P a ck i bi , .

R ose, Me t a llurg y of G ol , 1 902 , p . 4 94 .

 CHA PT ER X III
T HE A SS A Y OF OR E S A ND A LLOYS CON T A I N I N G P LA T
I N U M I R I D I U M G OLD , , , S I LV E R , E T C .

Ma te ri al s cont a i ni ng some the a bove elements a r e p re of

d d
sented to the a ss a yer fo r determin a ti o n in the sh a pe of sa nd s

cont a ining chiefly pl a tinum a lloys a n j ewelers sweeps a n ,

’
, ,

more ra rel y or es co nta ini ng pl a tinum in the form of the miner a l

.

d
sperrylite etc ,
.

T h e a ss a y for pl a tinum a n a ssoci a ted met al s is a di fficul t

o ne due t o t h e f a ct th a t in the p a rting of the pre cious met a l
‘

be a ds by a cids compl ex re a cti o ns t a ke pl a ce by which pl a tinum

d
, , , ,

p a ll a dium silver etc bo th g o into s olution a n a r e ret ai ned in

, ,
.
,

the residue unl ess cert a in w ell est a blished r a ti o s of met a ls

d
,

present a r e observed a n the p a rting opera tion rep ea ted severa l

times The a ll oys Of pl a tinum a n silver h a ve been most thor
. d
oughly inv estig a ted in this c o nnection 1
When the a lloy is .

more complex i e c o nt a ins a lso gold p a ll a dium iridium

,
. .
, , , ,

rhodium etc the di fficulties of the a ss a y a re incre a sed ; the d a ta

,
.
,

a t present a v a il a bl e a r e me a ger .

Pl a tinum nuggets from the U r al s cont a in : Pt 6 0 to

2
p er ,

per cent Ir up to 5 per cent ; R h up to

d
cent ; F e up t o
.
, .
,
.
,

4 p er cent ; Pd up to 2 p er cent ; a lso OS R u Cu A u a n iri

dmi m
.
, .
, , , ,

nd
os u .

When m a teri a l c o nt a i ni ng A u A g Rh Ru s a ,
Pt Pd Ir
,
O , , , , , ,

I r OS is fused by the cru cible a a

dthe
or a ss y melted with le d the ,

A u A g Pt Pd Ir R h Ir Os a r e collected by the le d
d
, , , ,
a an , ,

R u a n Os o nly p a rti a lly so

,
If the resul t a nt l ea d butto n is .

cupell ed the fin a l be a d will cont a in the A u A g Pt Pd Ir R h

d
a

d
, , , , , , ,

Ir Os a n a c o mp a r a tively sm a ll p o rt ion of the Os a n R u the

, ,

most of th ese t w o met al s bei ng lost by oxid a ti o n T h e presenc e

d
.

of a ny consider a ble a mounts Of Os a n R u in the le a d butt o n ,

1 T h om pso n an d
M iller , in J o ur . A m Ch em S oc
. . .
, X XVIII , 1 1 15 . S ee this pa per for
f
dA d
o th er r e er enc es.
“K emp , in E ng . an dM i n J our
. .
, LXXIII , 51 3 (No tes on Pl a tinum an sso cia te

Met a ls)
d
.

E x cl usiv e o f losses b y a bso r p tion a n v ola tili a tion z .

1 86
 T HE AS S AY OF O R E S A ND A LL OYS 187

owing to th e f a ct th a t they will not al loy re a dily c a uses them t o ,

a ppe a r a s a bl a ck scum o r a s spots o n the be a d ne a r the end of ,

the cupell a ti o n The presence of the pl a tinum gro up of met al s

.
,

r a ising the melting-point of the gold silver all o y renders neces -

,

s a ry a high tempera ture of cup ell a tion in order t o remove le a d .

E ven then whe n the r a tio of A g to Pt etc is les s th a n 5 to 1

, ,
.
, ,

le a d will be r et a ined in v a rying proporti o ns a t the cupell a ti on

tem p era ture o f gold b ullion To get rid of the le a d the pr op or .
,

ti on shoul d be 1 0 t o The foll o wing points on the first cu pell a

tion of the le a d buttons resul ting from the a ss a y o f m a teri a l ,

cont a ining Pt etc will give the a ss a yer a n ide a Of wh a t is

,
.
,

p resent When Pt a lone or with very little silver is present the

.
, ,

be a d from the cupell a tion (a t a comp a r a tively high tempera ture)

is rough dull gray fla t a n c o nt a ins le a d
, , , d .

If more silver is p resent but less th a n 2 p a r ts of A g t o 1 of

d
,

Pt the be a ds a r e rough fla t a n h a Ve a cryst a lline surf a c e

d
.
, , ,

If more th a n 2 p a rts of A g a re present a n not m o re th a n 1 5 ,

d
the be a d a ppro a ches more ne a rly the a pp ea r a nce o f a n o rm a l
s ilver be a d but h as a more steely a ppe a ra nce a n is fl a tter in
,

pr oportion to the Pt etc c o nt a ined ,

.
,
.

Bea ds c o nt aini ng m o re pl a tinum th a n 1 in 16 will not blick

or fla sh .
2

The eff ect on the a p pe a ra nce of the be a d of Pd R h Ir is si mil a r , ,

t o th a t of Pt but not identic a l ,

.

Owing to the di fficulty in a lloying iridium this when present , , ,

is a pt to be found a t th e botto m Of the b ea d in the sh a pe of ,

fine bl a ck cryst alline p a rticles “ .

T HE A CTION OF A CI D ON T HE A LL OY BE ADS — A gre a t de al

of liter a ture exists o n this point ; but most of it i s very conflict
ing ; some f a cts however h a ve b een definit ely est a blished
d d
, ,
.

N i tri c A ci — In a n a lloy of Pt a n A g tre a ted by HNO, ,

pl a tinum go es into solution in v a rious proportions depending

d
,

on the r a tio of A g to Pt a n pro b a bly t o some e x tent o n the ,

strength of a cid It h a s been st a ted th a t when the r a tio o f

.

A g t o Pt is 12 or 1 5 to 1 this s olution of Pt is complete in one ,

t r e a t ment but this h a s been disproved by l a ter investig a tion

,
‘
.

In o rder t o a ccomplish the solution o f Pt the a cid tre a tment ,

1 S h er w oo d , Cu pell a ti o n on Pla ti num A ll o ys , c o nta ini ng Ag an d A u, in J our . S oc .

Ch em I M ,
. . XXIII , NO 8 . .

2
S chifiner , in M i n I M , VIII
Of G d
. .
, 39 7 .

“
R Meta ll ur g y p 51 4
d
ose , ol , . .

T h o mpson a n Miller , in J o u r A m Ch em S oc . . . .
,
XXVI II , 1 15 .
1 88 A M A N UA L OF F I RE A S S A YI N G

must be r epe a ted a t le a st once or twice with a possible reOUpel ,

l a tion Of the residue with sil ver before the sec o nd tre a tm ent .

It is even th en d o ubtful if a ll of the Pt c a n be diss o lved T h e .

Pt goes into soluti on in the nitric a cid in c olloid a l form g iving ,

a brown to bl a ckish color to the soluti o n When gold is present .

in the silver pl a tinum all oy the solubility of the Pt seems t o

-
,

d
be decre a sed unless the r a tio of Pt to A u to A g is
1
,

when most but not a ll of the Pt a n a ll the A g g o into solu

, ,

tion P a ll a dium goes into solution with ni tric a cid when a t le a st

.

3 p a rts of A g to 1 Of Pd a r e present 8
yi elding a n ora nge c ol o red
-
,

so lution ; but double p a rting is necess a ry to insure complete so

lu t ion (.This point is n o t su ffici ently est a blished !
) The or a nge
c olored s olution indic a tes c olloid a l p a ll a dium
d
.

—
I ridium a n R h o dium Iridium present in the be a ds is
d
.

un a cted up o n by HN O, a n rem a ins with the gold 5

R hodium .

is slightly dissolved but most of it rem a ins with the gold Irid o s,
.

mium is not dissolved Osmium is dissolved R uthe ni um is . .

not dissolved
d d
.

S ul p huri c A ci — Pl a tinum a ll o yed with silver a n gold

d
, ,

c a n be sep a r a t ed from the silv er a n rem a ins with the gold if ,

c o ncentr a ted sulphuric a cid is used in p a rting In o rder t o .

insure th o ro ugh p a rting a t le a st 1 0 p a rts of silver t o 1 p a rt Pt

d d
,

an gold sh o uld be present a n d o uble p a rting resort ed to , ,

d
otherwise silver w ill rem a in with the residu e °
T h e p a rting in .

H,,S O4 le a ves the Pt a n gold in a very fine st a te of division (but

no t a s a coll o id ) some o f which is very a p t to be l o st in dec a nting
, ,

S O th a t it is best t o sep a r a t e by fi l t ering through a n a shl ess fil ter .

It is al so t o be noted th a t le a d m a y be present in consequence of

too lo w a cupell a tion temper a ture in whi ch c a se the residue should ,

be tre a ted with a mm o nium a c et a te to remove l ea d sulph a te ,

.

P a ll a dium In p a rting with H, S O4 this go es in to solution

— .

d
with the silver giving a n or a nge c ol o red soluti o n Whether this
,
- .

"
soluti o n is complete h a s no t a s yet been d emonstr a te
d d
,

Ir I r Os R h a n Os a n R u in the be a d a re not dissolved

d d
.
, , ,

N itr o Hy r ochlor i c A ci — F rom the residu e of the sul phu ri c

d
-

a cid p a r ting the Pt A u a n , a ny Pd left is d i ssolved by dilute

, ,

dd
d N
1 S h ar woc , ib i .

“
2
Lo A y p
y Of G dp
g e, o tes o n ssa i ng , . 21 5 .

“
3
R M
d N
”
ose, eta ll ur g ol , . 514 .

“
y pp A ssa ing
d
4 Lo g e, o tes o n , . 218, 219 .

5
R
d d
ose, ibi .

mp M
Ld d
T ho so n a n ill er , ibi .

7
o y p
g e h ol s th e c o ntr ar , . 21 9 .
1 90 A M A N UA L OF F I R E AS S A YI N G

tre a ted with 5 c c more Of a cid for 10 minute s

d
the residue
d
re- . .
,

d
an the residue a n a cid w a shed into the bea ker cont a inin g
the first a c id The a cid is then diluted a n the resid u e
d
.

se p a r a ted by fi l tr a ti o n through a sm a ll ashl ess fil ter a n thor ,

o ughl y w a shed with hot w a ter t o i nsure remov a l of A g , S O,

d
.

The filter p a per is d ried a n c a refully tra nsferred t o a po rcel a in

d
-

p a rting cup or a n a nne a ling cu p a n the c a rbon burnt OS in

-
,

the mu m e The a nne al ed residue is b rushed out o n the sc al e

d
.

d
f the be d b l nce weighed It consists of gold p l ti
d
p a n o a a a a n a .
,

num i ridium iridosmium rhodium a n p ossibly osmium a n

d
, , ,

R u (If a ny esc a ped oxid a tion during the cupell a tion) a n perh a p s
some p a ll a dium Its col o r will be gr a y or bl a ck if the ra re
.
,

met a ls a re present to a ny extent If not the ch a r a cterist ic gold .

,

c olor wil l show The p al l a dium is l a rgely in the filtr a te (It is

. .

question a ble h ow compl ete this soluti o n If i t h a s been

d
d
A g t o the cupell a ti o n to get the 1 0 to 1 r a ti o
d
u nnecess a ry to a ,

d
t h e di ff erence in weight between the origin a l be a d a n the weight
o f the residue represents the A g If sil ver h a t o be a dded a n d
d
.

d
the be a d recupelle the weight of the a dded silver plus th a t o f
,

the residue subtra cted fro m the weight of the r ecu pelle be a d
, ,

d
gives the silver A l l o w a nce must however be m a de for con
.
, ,

si er a b le loss of silver a s a result of high cupe ll a ti o n tem p er a ture .

d
If a ccur a te silver results a re required a duplic a te a ss a y on the ,

m a teri a l must be run a n the silver requisite to bring the r a tio

,

up to 1 0 to 1 is a dd ed a t once to the le a d bu tto n one cupell a tio n ,

O nly being m a de A t the s a me time this is run a check a ss a y

d
.
,

is run beside it m a de up of the s a me weight of le a d a n the

, ,

pro per weight o f sil ver i e the a mount a dded to the first c upel ,
. .
,

l a tion plus the a mount a ppro x im a tely kno w n to be in the a s sa y .

The loss in this will g ive the c o rrecti o n to be a dded to the a ss a y

for A g It m a y be d esir a bl e to determine A g in the w et w a y
. .

“
( S ee The A ss a y of S ilver Bullion .

The residue is no w wr a pped in 8 t o 1 0 gr a ms o f le a d foil with

a t le a st 20 times its w eight in silver a n cupelled a g a in a t a d
high temper a ture The b ea d if l a rge is roll ed out a n he a ted
.
, ,
d
to boiling in a m a ttra ss or fl a sk for 20 minutes with HNO,
d
,

sp gr . . a fter which the a cid is d ec a nted into a be a ker a n ,

the tre a tment repe a ted with HNOs Of sp g r The residue . .

,

d
if finely divided should no w be filtered thro ugh a n a shless filter
,

an w a shed a s a lre a dy described If no t the fil tr a te c a n be .

,

1 R i k tt
c end Mills a in N t s on A a ying
er ,sta t th t th Pd di
o e lv wi th th A g
ss ,
"
e a e sso es e .
 T HE AS S A Y OF O RE S A N D A LLOYS 191

d
d
dec a nted a n the residue w a shed The resi due c o nsists of A u
d d
.
,

Ir a n iridosmium a n some R h a n R u If there is a sus ,

.

p i cio n th a t a ny pl a tinum etc rem a ins the residue must b e ,

.
, ,

r e tre a ted with a cid until o f const a nt weight

- The pl a tinum is .

d
in the filtra te which will be colored brown or bl a ck ,
.

The di ff erence between the weights o f the first a n second

residues is pl a tinum the result possibly being somewh a t high if ,

p a ll a dium is p resent in the m a teri al a ss a yed The sec o nd residue .

d
is now w a rmed in a m a ttr a ss with dilut e a qu a regi a ( 1 to 5) 1

for 1 5 minutes This dissolves the gold some o f the R u a n

d
.
,

very little R h le a ving t h e Ir iridosmiu m a n R h with some

, , ,

Ru The residue is eith er fil tered or dec a nted a s necess a ry

d
.
, ,

dd
dried a nne a led a n w eighed The di ff erence in weight b etween
, ,
.

the second a n t hir residues represents gold somewh a t high if

d
, ,
'

the R u h a s p a rtly esc a ped oxid a tion a n vol a tiliz a tion during
cupell a tion The gold ca n be rec o vered by p reci p it a tion with
.

d
ox a lic a cid a s describ ed in the second method
,
.

If the third residue is tre a ted with strong a qu a re g i a a n ,

d d
boiled it dissolves out the iridium le a ving a s a residue the
, ,

d
iridosmium a n most of the R h This is dried a nneal ed a n .
, ,

weighed the di fference in weight between the third a n fourth

d
,

residues repres enting iridium a n the weight of the fourth residue

d
,

representing irid o smium a n R h The method determines A g

d
.
,

Pt A u Ir a n irid o smium plus R h The prob a ble errors in

, , , .

the determin a tion h a ve been pointed out P a ll a dium c a n b e .

s a tisf a ctorily determ ined only by w et a n a lysis

d d
.

S econ M etho 2—

d
T a ke the l ea d button from the o re or
.

a lloy a ss a y a n scorify a t a high he a t with a dditi o n al test le a d

, , ,

if necess a ry to a weight Of 8 to 1 0 gra ms It should cont ai n

, .

les s th a n 5 p er cent Pt et c in order t o be m a ll ea bl e R oll

d
. . . .
,

o u t the butt o n into a l o ng thin fill et a n pl a ce in a l a rge be a ker

with 200 c c o f HN0 3 sp g r a n he a t until a ll a ction ce a ses d
d
. . . . .
,

Filter through a sm a ll a shless fil ter a n w a sh the residue with

d
d
hot w a ter D ry the residue a n p a per , tr a nsfer to a l a rge size
d
-
.

p a rting cup a n igni te in the mu ffie to burn off t h e c a rbon a n

-
, ,

oxidiz e a ny Pb not disso lved Then he a t t o b oiling in the cup .

with HNO,
d
sp gr d ec a nt w a sh th o roughly with hot w a ter
,
. .
, ,

dry a nneal a n weigh the residue This consists of A u Pt Ir

d d
, , .
, , ,

irid o smium a n most o f the R h a s well a s the R u a n Os which

d dp
, ,

1 Co ncentr a te aq ua r eg ia is 1 p ar t HN Os. sp g r . . an 3 art s HCl , sp . gr .

H Q XVII
d d
3
E Miller , in S chool of M i nes ua r t ,
. .
, 26 . .

8 1 pa r ts istille HzO to 1 9 p ar ts HNOs cone (sp g r . . .

1 92 A M A N UA L OF F I RE A S S A YI N G

d
sc a p ed oxid a tion a n vol a tiliz a tion du ring the scorifica tion
d d
e .

The fil tr a te cont a ins the A g a n Pd a n a little o f the R h

d
.

R epl a ce the residue in the c a psul e a n w a rm (not bo il ) wi th

'

dilute a qu a regi a ( 1 to 5) fo r 1 0 minutes This dissolv es th e

d
.

d
A u a n Pt D ec a nt the soluti o n into a sm a ll be a ker w a sh the
d
.
,

d d
residue ry a nne a l a n weigh The sec o nd residue consists of
, , ,
.

Ir Ir Os R h a n a little Os a n R u This residue is boiled

d d
.
, , ,

with strong a qu a regi a which dissolves the Ir a n some Os an

d d
,

R u a n le a ves in the third residue the I r Os a n R h with a little

d d
, ,

Os a n R u Thi s is w a shed dec a nted a n weighed a s before

.
, ,
.

The filtr a te fro m the tre a tment Of the first r esidue which co n ,

t a ins the gold is ev a por a ted j ust t o d ryness but not b a ked so
, , ,

d
a s to prev ent reducti o n Of the gold c hl o r ide t a ken up with dis

d
,

tilled w a ter a n a drop of HCl a n the gold in it precipit a ted by ,

w a r ming with cryst al s of o x a lic a cid for a h al f h o ur filtering

d
, ,

drying the yell o w coherent precipit a te Of gold This is

d
an .

tra nsferred filter p a per a n a ll t o a piece of sheet le a d silver

,
-
, ,

a dded t o the weight o f 3 times the gold pres ent a ppr o xim a tely

d d
, ,

cu p elled the be a d being p a rted in HNO, a s usu a l a n the

d
an ,

gold a nne a led a n weighed The weight of the gold subtra cted
d
.
,

fro m the di ff erence in weight b etween t h e first a n s econd residue s

is the pl a tinum This l a st m a y a lso be estim a ted by destroying
d
.

the o x al ic a cid in t h e filtra te fro m the sep a r a tion of gold a n pre ,

cipit a t ing as

It is to be no ted th a t by the a ss a y a s outlined neither o smium

, ,

nor ruth enium ca n b e d et ermined o wing t o their vol a tility d ur ing ,

p a rt of the oper a tion ; th a t p al l a dium c a nn o t be re a dily deter

mined o wing t o its v a rying solubility ; a n th a t when rh o dium
,
d .

o r the a bove met a ls a re present in a ny a ppreci a ble qu a ntity ,

d
some of the results o bt a ined a r e li a ble to err o r R hodium
d
.
,

o smium a n ruthenium a r e a m o ng the r a rer of t h e group a n

, ,

a r e frequently a bsent The methods o utlined will serve t o

d
.

determine re a s o n a bly well pl a tinum gold silver iridium a n , , , ,

iri dos mium plus rh o dium When the o th er elem ents of the gro up .

a r e pre sent wet methods not within the sc o pe of this bo o k

, , ,

d
must be resorted to .

In the ordin a ry a ss a y as c a rried ou t fo r gold a n s ilver

d
, ,

pl a tinum a n p a ll a dium m a y esc a p e the a ss a yer if present in

o nl y sm a ll qu a ntities fo r obvi o us re a sons P a rting in sulphuri c
, .

2
a cid is theref o re necess a ry to determine whether they a r e present

d
.

“
Croo kes, S el ec t M eth o s
d d dm
1 .

A n or a ng e-colore solution in ica tes palla iu .

1 94 A M A N UA L OF FI RE A SSA YI N G

while the S nO, p asses through the lower st a g e of oxid a tion in

being reduced to meta llic tin .

d
6 The c a ssiterite before reducti o n is a p t to c o mbine with
.
, ,

b a sic fluxes present in the a ss a y a n be c a rried into the sl a g a s ,

st a nn a tes .

F rom this therefore it is evident th a t the fire assa y fo r tin is

, ,

d
only a n a pproxim a ti o n al though in m a ny c ases a ver y cl o se o ne
, .

If the resul t on a tin ore by the fire metho chec ks th a t of t h e

st a nd a rd wet method (the modified R o se it is t o b e
a scribed to a b al a ncing Of errors due to the presence of o th er ,

met a ls in the o re which h a ve been reduced into the tin button

,
.

Pr epa r a tion of the Or e f or A ssa y —It is essenti al t o remove

d
.

a ll the g a ngu e of the o r e a n h a ve for t he a ssa y nothing but t h e

c a ssiterite a s fa r a s this is p ossible The o re is roughly cru shed
d
.
,

put through a 4 0—mesh sc r een cru sh ing s

d
o n a buck bo a rd a n ,

an screenings succeeding e a ch other a t frequent interv al s in

“ ”
o rder to a void the sliming of the c a ssiterite If the o re is .

d
lo w gr a de i e bel o w 2 per cent
-
,
. .
, SD 1 000 g r a m s of t h e .
,

crushed o r e is weighed out a n c a refully p a nned in a gold p a n ,

the first p a nnings bein g sa ved fo r r ep a nning The ore is .

c oncentr a ted j ust a s much a s p ossible with o ut incurring loss

'

of c a ssiterite The concentr a tes from the rep a nning of t h e

.

t a ilings o f the first tre a tment a r e a dded to the m a in lot Of co n

cent r a t es S ome or a ll of these will unless the ore is very pure
.
, ,

c o nt a in p rob a bly g a rnets feldsp a r tourm aline m a gnetite , , , ,

zirc o ns wolfr a mite c olumb ite sulphides qu a rtz et c T h e

d
.
, , , , ,

c o ncentra tes a r e c a refully tra nsfe r red t o a porcel a in dish ried

d
, ,

ro a sted a t a bright red he a t in order to decompose sul phides

d
an -

an sul ph a tes Whil e t he concentra tes a r e still red hot they

.
-
,

d d
a r e tr a nsferred into a be a ker cont a ining w a ter in order t o m a k e

g a rnet a n other silic a tes s oluble (al l except uv ar o vite) a n ,

a fter dec a nting w a t er tre a ted with nitro hydrochloric a cid to

-
,

rem o ve most of the c o nt a min a ting miner al s except qu a rtz

d
, ,

wolfra mite a n some g a rnet The c o ncentra tes a r e then fil

d d
.
,

d
t er e Off a n dried If qu a rtz is present this ca n be removed by
.
,

tr a nsferring the fil tered c o ncentr a tes t o a pl a tinum dish a n

tre a ting with HF Thi s however will r a rely be nece ss a ry T he
.
, ,
.

c oncentr a tes a r e then c r ushed in a n a g a te mort a r t o p a ss a 1 00

mesh screen a n tre a ted as desc ribed below

—
d .

T he A ssa y T h e two b est methods for a ss a y a r e the cy a nid e

1 H fm n T h Dry A a y Of T in O
o a , e in T a ns A I M E XVIII 1
ss res, r . . . . . .
 T HE AS S A Y OF T I N , M E RCUR Y L E A D
, ,
ET C . 1 95

d
fusion a n the G erm a n method with bl a ck flux sub stitute , .

Of these t w o the cy a nide fusi o n is gener a lly to be p r eferred a s

, ,

a ny miner al s still left in the c a ssiterite h a ve l ess influence on the

a ss a y a n
,
d
the l o ss of tin by vol a tiliz a ti o n is reduced t o a mini
mum o n a ccount of the l o w temp er a ture employed
d
.
,
1—
T he Cya ni e F usi on I t is essenti a l t o use o nl y the purest
.

—
cy a nid e obt a ina ble the best sodium or pot a ssium cy a nide o n
the m a rket for use in the cy a ni de process S uch impurities a s
d
.

K, CO, sul p h a tes a n sulphides in cy a nid e c a use s eri o us loss es in

, ,

the a ss a y The b est a lk a line cy a nide to use is sodium cy a nide

.
,

which m a y re a dily be pro cured a t the present time S o me o f .

“
the ordin a ry commerci al cy a nid e known a s pot a ssium cy a nide
fuses a t such a lo w tempera ture th a t the c o nc entra tes sink t o
d
.

d
the botto m of the crucible befo re reducti o n a n wh en reduction ,

d
fin a lly t a kes pl a ce the little gl o b ul es of tin a r e foun to be very
i fficult to collect In o rder th a t the fusion m a y b e succ essful
.
,

it is essenti a l t o fo ll o w directions clos ely It is best to Use 1 0 .

gr a ms o f conc entr a tes o r a n a mount nea r th a t ; usu a lly the ,

a mount of conc entr a t es obt a ined fro m the c o ncentr a ti o n of t h e

o re a ppro xim a t es this if the prop er a mount of ore is ch o sen fo r

conc entr a tion T W O gr a ms of powdered cy a nide a re firmly

.

d
t a m ped into a 20 gra m crucible the c o ncentra tes a re mi x ed
-
,

with 3 0 gra ms m o re of cya ni d e pl a c ed in the c rucibl e a n , ,

covered wi th 5 gr a ms more The cru cibles a r e pl a c ed in the

d
.

mu ffie a t a full red he a t ( 750 an -

a r e ke p t a t this temper
°

d
a ture fo r a b o ut 1 5 to 2 0 minutes The ch a rge will become very .

liquid a n will be a b o wn red The temper a ture should no t

d
r - .
,

be so high a s to c a use the cy a nide to boil a n ev olve h ea vy

fumes It m a y how ever be kept t oo l o w in which c a se the
d
, ,
.
,

chemic a l re a ctions will no t c o mplete themselves a n the tin

will f a il to c ollect into a button If the concentr a tes still con .

t a in so me foreign miner a ls the fusi o n t a kes l o nger th a n 20

d
,

minutes The c rucibl es a r e th en withd r a wn c o oled a n the

.
, ,

butt o n recovered by bre a king t h e c rucible There will be t w o .

distinct sl a gs the l o wer o ne surro unding the button usu a lly

d d
, , ,

d
light green a morph o us a n subtra nsluc ent a n the upper one ,
, ,

o r fused cy a nide o p a que milk white a n c o a rsely gr a nul a r

d
-
, , ,

soluble in w a ter The tin button should be white a n soft ; if

.

not it cont a ins foreign met a ls

d
.
,

T he G er ma n M etho — The G erm a n method is b a sed o n t h e

.

1 HOIM s {bit} .
1 96 A M A N UA L OF F I RE ASS AYI N G

fusion Of t h e c a ssiterite concentr a tes with ch a rc oal a n bla c k d

flux substitute which h a s the com p ositio n 2 p a rts K, CO, 1 p a rt
, , ,

flour Five gra ms o f the concentra tes a re inti ma tely m ixed wit h
d d
.

1 g ra m of pu re w o od c h a rc o a l a n p ut into a N o D le a c r u cibl e o r .

—
a n ord i n a ry 20 gr a m c r ucible On top Of thi s are p l a ced 1 5 g ra ms
.

o f bl a ck flux substi tute with which gr a ms bor ax g l a s s h a ve

d
,

bee n mixed Fin al ly a pure s a lt c o ver is a dded a n a piec e of

.
,

d
c h a rc o a l the crucible covered with a cl a y cover pl a ced in t h e
, ,

m uffle a n hea ted a t a mod era te hea t until boili ng of the ch a rge
d
,

h a s e a sed a
c n then o o h a lf to thre qu a rters Of a n hour
,
f r n e- e-

more a t a white he a t The crucible is then removed from t he

d
.

mu m e a llowed to c oo l a n bro ken fo r the tin button This

d
.
, ,

sh o ul d b e white a n soft a s in the cya nide fusion

‘

.
,

D uring the fusion as t h e temp er a ture ri ses the ch a rco a l

, ,

reduces t he st a nnic o x ide to met a llic tin while a ny ferric o x id e

d
,

is reduced to ferrous o x ide if the h ea ting is gr a du a l a n is ta ke n , ,

up by the sl a g A s the temp era ture rises the fl o ur in the bl a c k

.
,

flux sub stitute p a rti a lly decomposes libera ting c a rbon throu g h ,

o u t the ch a rge which a s fusi o n t a kes pl a ce p revents a ny st a nni c

, , ,

o x ide not as yet reduced fro m uniting with the a lk al i of t h e

flux The sl a g a fter c o oling should be crushed a n p a nned fo r

.
, ,
d
d
a ny prills Of tin which h a ve not entered the button Th ese a re .

weighed a n a dd ed to the weight of the button .

R esults Obta i na ble —

d
Bl a ck H ills c a ssiterit e concentr a tes
.
,

ro a sted quenched a n tre a ted with nitrO hydrochlori c a cid

,
-
,
1
.

Wet met ho d of R ose-Ch a u venet

K , CO, Sn
d
wi t h p er c ent .

G er ma n met ho 67 58 per cent S n .

per cent . Sn

S tre a m tin from D ur a ngo Mexico , ,

2

Wet method ( R ose) 65 62 per

. c ent . Sn
G er ma n m et h o d .
p er cent . Sn
Cya nide meth od . 65 1 9 per cent . Sn

It is to be noted th a t while the dry methods a ppro a ch very

clos ely to t h e wet a n al ysis wh ich gives the a ctu al tin in the ore , ,

the dry a ss a y r esults a re due more o r less to a b a l a ncing o f errors

d
.

F requently ry a ss a ys will give higher resul ts th a n the a n al ysis ;

this is due usu al ly to reduced iron .

1 Ho fma n ibid , .

E H Miller T h e Assa y of T in O res

. .
“
, ,
"
in S chool of M i nes Q ua r t .
, X I II , No 4 . .
1 98 A MA N UA L OF F I R E AS S A YI N G

d
should p a ll ass a 40-mesh
s creen A select lot of filing s a re best .

digested with al c o hol fo r som e time t o remove o il a n gre a se ,

then he a ted in a mu ffl e to a d ul l red he a t for 1 0 minutes c o oled

d
-
, ,

stored in a tight bottle It is essenti al t o h a ve the filings

d
an .

free fro m o il a n gre ase else this will be deposited o n the silver
,

fOil with th e mercury The a mount of mercury in the ore should

.

not be so g re at a s t o c a use to o he a vy a co a t o n the silver foil - .

F or high gr a de or es not more th a n

- to ,
gr a m should be
u sed V ery sm a ll a mounts Of mercury ca n be detected by this
.

method .

T h e o re mixed with filings is pl a ced in the a nne a ling cu p

, , ,

d
which is set into t h e a sbest o s bo a rd on the ring st a nd the sil ver -
,

fOil weighed a ccur a t ely a fter i g niting t o within mg a n

d
,
.
, ,

fit t ed to the cup a n t h e silv er dish fil led with c old w a ter pl a ced

, , ,

on the foil T h e a lc o h ol fl a me is then a llowed t o pl a y j ust on

.

the botto m of the cu p but no t to spre a d a ro und the sides T h e

d
.
,

fl a me should be a bout in high a n is b est shielded by a .

screen t o ste a dy it The b ottom Of the c rucible sho ul d no t

.

bec o me more th a n a dull red o therwise mercury will esc a pe ,

c o ndens a t ion The time Of he a ting should be from 1 0 t o 1 5

.

minutes It is best to h ea t f o r a bout 1 0 m inutes th en cool

d
,
.
,

d
an rehe a t fo r 3 to 5 minutes Longer he a ting th a n this c a uses .

l o ss of mercury T h e degree a n time Of h ea t a r e very import a n t

. .

D uring t h e h ea ting t h e w a ter in the dish sh o uld be repl a ced

o nc e o r twic e It ca n e a sily be removed by a b ent tube th a t
.

h a s been filled with w a ter a cting a s a siphon While the w a rm ,

.

w a ter is being remo ved c old w a ter is a dd ed from a w a sh bottle

,
- .

d
A fter the pro per he a ting the a lcoh ol l a mp is removed t h e a ss a y , ,

al l o wed to c o ol so mewh a t t h e silver dish removed a n the , ,

d
silver f o il with t h e m ercury tra nsferred by f o r c eps t o a desicc a tor
-

then weighed The diff erence in th e weight of the foil a fter

d
an .

an befo re the a ss a y is the weight of the m ercury fr o m which ,

the percent a ge is c a lcul a ted The fo il c a n be used a g a in a ft er .

driving Off the H g a t a red he a t in t h e muffle o r with a Bunsen ,

burner A piece of foil c a n be used a b o ut six times It should

. .

be weighed befo re e a ch a ss a y The m eth o d a lso s erves as a very

d
.

sensitive a n e a sily a pplied qu a lit a tive test on o res .

T h e following figures will serve to show the a ccur a cy o f t he

method : 1

G . N B ach el
. d
er , in S chool of M i nes Q ua r t .
, XX III , 98 .
 T HE AS S A Y OF T I N , M E RCURY L E A D , ,
ET C .

BY E L E CTR OLY S IS FR OM CY A N I D E BY CHI S M

’
s ME THOD
S OLU TI ON
p er cent .
per cent .

p er cent .
p er cent .

The a ccom p a nying illustr a tion (Fig 60) shows the a p p a r a tu s .

em p loyed .

T HE A SSAY OF LE A D OR ES — The fire a ss a y of le a d ores w ill

p rob a bly p a ss out Of use i n time j u st as the fire assa y of copper ,

h a s done A t the p resent time it is still l a rgely used al th o ugh

.
,

for com p l ex ores cont a ining much co pp er or bismuth or a ntimony ,

with t h e le a d it is not in vog ue

, It is however still th e criterio n .
, ,

FI G . 60 —.A P PA R A T 0 s RE Q U IR E D F OR T HE ME R CU R Y AS S A Y .

in t h e purch a se of p ure s ul p hide a n oxidized le a d ores a n al so d , d

such complex ores as furnished by the Le a dville Color a do , ,

d
distri ct U noxidized ores Of this type cont a in p yrite blende
.
, ,

g alen a s o me little ch a lcopyrite a n g a ngue Oxidiz ed ores

d
,
.

cont a in cer r u site a nglesite c a l a mine limo nite etc a n g a ng ue

, , , ,
.
,
.

The Obj ect of the a ss a y i s t o bring the le a d o f these ores down

into a button fr ee from other b a se met a ls such a s Cu Z n Bi
d d
, , , , ,

S b F e a n free al so from S a n A s The loss of le a d by v ol a tili

d d
, , .

z a t ion a n sl a gging a n the reduction of b a se met al s should be

kept to a minimum A s al re a dy st a ted this is a di fficult thin g
.
,
200 A M A N UA L OF F I RE AS S A YI N G

d
to o ; so th a t pure ores will inv a ri a bly give lo w results a n , d
impure ones hi gh .

Th ere a re three method s Of a ss a y diff ering in the flux u sed ; ,

( )
1 the le a d flux method ; ( )
2 the sod a a rgol method ; ( )
3 the -

cy a nide fusion Of these the l ea d flux method is chiefly used

.
,

thro ughout the West The so d a a rgol method is a go od o ne on .

-

o r es no t b a sic The cy a nide method is onl y a pplic a bl e to pure

.

ores With impure ores it tend s to red uce other b a se met als
.
,

due to its powerful reducing a cti o n V a rious mixtures o f le a d .

flu x a r e used of which three a r e m a de up as follows :

,

NO 1 . No 2 . No 3 .

pa rts Na HCO pa Na HCO, pa rts N HCO, H

'

4 2 r ts a / 7_
, ,

4 pa r ts K OO , , 2 pa r ts K OO , , 5 pa rts K CO , ,

2 pa rt s fl our 1 p a r t fl o ur pa r ts flo ur
1 pa rt bor a x gla ss 1 pa rt bora x gla ss pa rts bora x gla ss
y9 ,

1 h ‘l
Flu x N o 3 is prob a bly the best for m ost purposes a s deter
.
,

mined on a series Of ores the results with it being slightly higher 1

, .

For ass a y 1 0 gr a ms Of ore ( 1 00 mesh fine) a re mixed with 3 0

,
-

d
gr a ms of flux p l a c ed in a N O 6 or D crucibl e o r in a 20 gr a m
,
- .
,

c rucible covered with 8 gr a ms more of flu x a n put into the

, ,

mu m e a t a low he a t which is th en r a ised to a light yellow ( 1080 ,

°

The fusion S h o uld t a ke a b o ut 30 t o 3 5 minutes N a ils

'
.

a r e a dd ed to the ch a rge two tenp enny n a ils fo r he a vy sulph i des , ,

o ne for light sulphides or o xidized ores When t h e ch a rge is .

t a ken from the muffle th e n a ils a r e rem o ved from the cru cibl e ,

by a p a ir of short h a nd t o ngs c a re being t a ken to w a sh o ff all

d
,

a dhe ri ng le a d gl o bules The crucible is th en sh a ken a n t a pped

d
.

d
thoro ughl y a n p o ured The l ea d butto ns a r e cle a ned by
,
.

h a mmering a n then weighed The percent a ge is o bt a ined b y .

mul tiplying by 1 0 .

T h e r ea flions in the crucibl e a re a s follows

7Pb s 4 K, CO, 4 Pb 3 ( K, S , Pb s) K, S O, 40 0 ,
K, S Pbs + Fe Pb K, S
, FeS
2Pb O C 2Pb CO2

T he
c a rbon lib er a ted in finely divided p a rticles from t he
flour on he a ting reduc es a ny le a d o xides o r c a rbon a tes in t h e o re
d
,

whil e the iron reduces le a d fro m its sulp h ides a n sul ph a tes .

The a ss a y should ch eck (in triplic a te) within per cent .

1 M cE lv enny an d
I sett , in T h e Ch emic a l an d
F ir e Meth o dD
s of eter mining Lea d
O res,

M i n R ep .
, X L VIII , 26 .
 A P PE ND I X 203

8 $ $ 8 8 8
8 8 8 A
8 s 8
.

° 8 o 8 8 8
a

8 8 8
8 8
A

$ 8
8 8
a

8 s 8
8 8 a
a

8
.

8 8

a 8 $
8 8 2 8
a

8
8
6
8
204 A MA N UA L OF F I R E AS S A YI N G
TA BL E XLIII .
— FI NE NE SS OF B ULLI O N AN D ALLOY S OF
PR E CIO US ME TAL S

One ca r a t 4 1 666
24 ca r a ts 1 d
poun tro y (E ng la n ) d
m a r k ( G er m a ny e tc )
. .

24 c a r a ts 1 , .

g r a ms 1 m a re of 8 o u nces (Fr a nce

One m ar c
,
g r a in p er
S p a in, et c .
)
One o u nce p er m ar e 8 o u nc es 1 ma r c (F n S p in
ra ce , a , e tc .
)
One lo th (sil ver ) 1 6 l o th 1 ma r k (G m ny t )
er a , e c .

TA BL E XLI V .
— V OL UME A N D WE I G HT OF FI NE G OLD AN D
S I LVE R

Fine S il ver
Weig h t : g r a ms

W eig h t : y o u nces
tr o

Fin G ld
e o

W ig h t g
e : ra ms
W ig h t t
e : r o y o u nc es

V a l ue : po un ds ste r ling .

The foregoing t a bles a r e due t o Mr W J S h a r wo o a n were dd

d
. . .

fi r st publi sh ed in M i nes a n M i ner a ls XXI X 2 50 , ,

.

Ba ses of Comp u ta ti on — The gr a m is t a ken as gr a ins .

The v al ue o f a tro y o unce o f fine gold is a ssumed a s being ex a ctly

inste a d Of resulting in a n error of l ess .

th a n o ne in V a lu es in E nglish coin a r e b a sed On t h e

a ssum ption th a t a n ounc e of fine gold is worth p o und sster
ling o r 8 5 shillings
,
p ence ; this is t oo high by a b o ut o ne
,

p a rt in the t rue v a lue b eing p ence It is usel es s .

to a ttempt a cl o ser a ppro x im a ti o n in pr a ctic a l work for the ,

simple re a son th a t gold bulli o n a ss a ys a r e r a rely rep o rted cl o ser

th a n the ne a re st h a lf milli eme o r to within o ne p a rt in ,

d
A t the v a lues a d o pted o ne d oll a r is equiv a lent to S hillings ,

o ne pound sterling to 34 8 6 3 53

d
an .

F or eig n a n Obsolete V a l u es — The a d a rme gr a ins o r 1 51

Of the S p a nish ounc e) sometim es used b y Mex ic a ns c olloqui a lly

,
 NA ME
d
PA G E
Allen Hillebra nd a n Allen
dB i
, E T . .
, see .

Ames an l ss

A nderson, 0 A
d
.

A usti n a n H u nter

B a chel d er , G . N .

B a i la r J C , .

B a lli ng C
d
,

B a nnister a n S ta nley
B a rt o n W H , .

B ette! W ,

B ow ma n F C
d
, .

B ow ma n a n Ma son
B runton W D , .

B ull I T
, .

B ullens D K , .

Ca rter T L “
d
dA
, . .

Chi ey,

Ch i sm , R . E .

Cla rk , A J .

Clennell, J . E .

Co llins
C r a w fo r d H
d
, C . .

Da y A
dh p
an llen
Da y an S e ar d
Dew ey F P , . .

D oslt z , O
d m
.

D oeltz G ra u
dh
an a nn

D
d
onna n a n S aw

E g W h
dm dH K
a er a n el c

E a n s, . .

Flinn F B , . .

Fried ri ch ,K .

H
d
Ful to n, C . . 86,
Go sha ll L D , . .

G ot tscha lk V H
'

, .

G uertler , W

Hil leb r a n W F
HOfm an H O
d , . .
, an d
A llen 128 , 1 3 2, 1 3 7, 1 64 , 1 65 ,

d
, . 1 1 7,
Hollow a y an P ea rse
208 I N DE x To AU T H O R S

Nm

Holt an d
C i h r stensen 7 9 , 1 06
Ho w e H M , . 9 4 , 1 02
Hunt F F , . . 1 26
Hunto on L D
d
, . . 40
I z et t an M c E l venny 200
Ja mes G A ,
. . 3 9, 1 9 7
J a nin Jr Lo uis
, .
, 6
Jolly H R , . . 1 59
Ka ufma n W H , . . 160 , 1 62
Keller E d w a r d , 19 , 4 1 , 1 07
Kemp J F , . . 1 86
Kerl B , . 76
K i t t o Wm , . 14 6
Koenig G A , . . 1
La y, F . 144
Leu b er Vi c t , . 1 72
Liddell D M , . . 4 1 , 4 7 , 1 05 , 1 62
L odge R W
d
, . . 1 1 8 , 1 1 9 , 1 4 7 , 1 6 1 , 1 64 , 1 6 7 , 1 68 , 1 88
Ma so n a n B ow ma n 1 60
McCa ug h c y W J , . . 1 29
Merr itt J W , . 7 9 , 1 06
Miller E H , 54 . .
, 59 , 1 1 6 , 1 20, 160, 1 68 , 1 69 , 1 8 6 , 1 8 7 , 1 8 8 , 1 9 1 , 1 9 6
Most o witsch W1 , . 2 8 , 64 , 6 5, 9 0, 9 1
N ut ter , E . H . 6
O rto n E , . 24
O stw a ld W , 48
Pa c k J W , . . 18 1
Perki ns W G , . . 1 1 6, 14 0, 1 4 2
R ber ts G M
o , . . 41
R obert s Au ste n
— 29 , 93
R oos, A T . . 1 53
R ose, J . G . 33
R ose, T K . .

S a nder , K .

S ch na bel C , .

S chi ff ner , M
dW J
.

S h a rw o o
d d
, . .

S hepa r Da y
d
an

mm
d
S ch o r le er a n R o sco e
S ievert s H g an a ena c k er
S mi t h , E .

S mi t h , E A . .

S mi t h , F . C .

S mi th , S . W .

S ulma n, H L . .

Ta ylor , E H . .

Th o mpso n T ,
.
 I ND E X

Acc ura cy of th e gold-si lver a ssa y

Al t erna te sh o vel m eth od Of sa m pling
Alum ina
Ama lga m a t io n Test
Ana lysi s o f bo ne a sh
o f co pper ma tte
o f h em a t i t e

o f fine si l ver .

o f fir e cla y fo r c r u ci bles

o f lea d a nt im o ni a l o res
-

o f li m esto ne

of sh eep a n d
ca tt le b o nes

o f si li ci o u s o r es

d
Antim ony beha v i o r of in roa st ing
, ,

o res a ssa y o f
, .

Ant i mo nia l o res m et h o of a ssa y o f

,

Ar g o l
red u ci ng p o w er o f

Arseni c beh a vi o r of in r oa st ing

, ,

Arseni ca l o res m et ho d of a ssa y of

,

ni ck el co lla lt sil ver-o res

-

m et h o d o f a ssa y of
Assa y b a la nce

i t a b le o f
va l u a t o ns,

Assa yi ng defi ni tio n o f

,

Assa y t o n syst em o f w eigh ts

-

B a la nces
i
co nst r u c t o n o f

for w eighing p ulp

no n co l um n t y pe of
-

p ra ct i ca l no tes o n
t heo r y o f
B a si c ores
Bism ut h o r es a ssa y , of

B la ck flux
su b st i t ute
2 12 I N DE x

B lister Co pper , meth o d o f a ssa y of

sa m pli ng of
Bone a sh a na lysi s of
,

scr een-a na ly si s o f

B o r a t es .

B or a x
gla ss
infl uence of on a ssa y
m elting p o i nt of
B o ri c a cid
B ulli o n a ssa y of
,

cla ssifi ca t i o n o f

fineness of
B ur ners Ca se t y pe
,

co nsu m p t i o n Of Oil by

fo r ga so lene
S i ze o f

f or Oil

fo r g a s
p ressu r e of ga so lene in

Ca r y b u r ner 14
Ca se g a so lene b u rner 15
Ch a r co a l 32
red u cing po w er of 54
tem per a t u re a t w hi ch r ea ct io n beg I nS W I th 59
u se o f i n r o a st i ng
, 1 14
Ch eck a ssa y
Chi sm s m et h o d fo r m er c u r y
’

d
197
Co ning a n q u a r t ering sa m p li ng by , 37
Co nt r o l a ssa ys 39
Co m bina ti o n meth o d of a ssa y
f or c ya nid e p r eci pi t a t es
pr eca u t io ns t o b e Ob ser ved in 1 28
Co pper m a t tes m et h o d Of a ssa y o f
, 1 27
r esu lt s o n 14 1
m et h o d o f a ssa y Of bli st er

sa mpling b li st er
of . 41
Co pper b ea r i ng m a te r ia l
-
, a ssa y of
lo sses I n a ssa y 1 69
Co st o f f uel fo r a ssa yi ng
Cr u cib les 24
B a t tersea 25
ca p a ci t y Of 25
dom esti c 25
fire cla y fo r
h 25
2 14 I N DE x

Ex cess li t ha r ge met h o d
r esu lts o b ta ina b le fr o m

Ferri c ox ide
F lo u r
re d ucing po w er of
Flu o r spa r
in t h e rea ssa y of c u pels
F u r na ces ca pa cit y Of
d
,

c o m bi na ti o n p o t a n m u ms
fo r a ssa yi ng
for b u rni ng coa l
co k e

g a s

w oo d
fuel consu m ption in
g ene fire
a so l - d
t em pe ra t u re a tt a ina b le in
F u rna ce t o ngs
to o ls
a nnea li ng-c up t ra y

cu pel cha r ging devi ce

-

c u p el t r a y
-

m o ld s
mult ip le sco rifier t o ngs

G a solene fu el in a ssa yi ng
as

G er m a n m et h o d o f a ssa y fo r t in
G o ld lo sses of d u r i ng cu pella t i o n
,

o ccl u d ed g a ses

prepa ra tion of p r oof

sil ver ret a i ned by a ft er pa r ti ng

so l u t i o n o f by a cid

d
w eigh t a n vo l um e of fine
G o ld b ulli o n
a ssa y Of

d
f or sil ver in
su r ch a r ge In a ssa y o f

o res co nta i ni ng
“ free gol a ssa y Of ,

-sil ver a llo ys losses d u r i ng c u p ella t io n

,

G r a p hi t i c m a teria l m et h o d of a ssa y f or
, .

Hema tit e , eff ect o f in o r es

 I N DEx 215

I m p u ri t y d efi ni t i on of
,

I m p ur i t ies in o res
I nq ua r ta t i on
I ridi um d etermina ti on Of
,

eff ect Of a c ids on

in pla t inu m nu ggets
I r on a ssa y of m eta lli c
,

na il met h o d
r ea c t ions in

Jones rifl e sa m pler

Lea d
b ulli on a ssa y of
,

sa m p ling o f

flux
o res, a ssa y of

fl ux es u sed in a ssa y of
r eact i o ns d
u r Ing a ssa y o f

r esult s Ob ta ined in a ssa y

sili ca t es

for ma t io n of in r oa st ing
m elt i ng p o int Of
-

re d u cti o n o f

Li me
Li tha r ge
m eltIng -p o I nt Of

d u ct i o n o f
d
re

r eq ui r ed t o f u se m et a lli c

d
ox 1 es

sil ver a n gold in

L uting ma teria l

Ma tte pro du ced in cru cible a ssa y

Mer cur y a ssa y o f
,

r esu lts Ob ta i ned in

Meth o d Of a ssa y f or a nti mony

for bism u t h
for co pper bea ring ma teri a l
fo r cy a nide so lut i ons
f o r fr ee go ld o r es
fo r lea d
fo r m er cur y
216 I NDE x

f or pla ti num ores

fo r tellu ride or es
f or t in
Metho ds of a ssa y
co m bi na t i o n m et h o d

co m p a ri so n Of

c ya ni d e m eth o d

i ron na il
Miller s o x ide sl a g met ho
’
d

d
niter m et h o d
ni t er i r o n met h o d
-

Per ki ns ex cess li tha r ge m etho

’

r oa st i ng m et h o d

sco rifica t io n m et h o d

Miller s ox ide sla g met ho d

’

M o ld s
Mu mes m et h o d of su ppor t of
,

si ze o f

Niter
i r on m eth o d of a ssa y
m a nner of a ct i o n of
meth o d of a ssa y
o x idi zi ng p o w er of

a ga i nst v a r i o u s r ed u ci ng a gent s

va r i a t i o n Of o x idi z i ng p o w er o f

Nit ri c a cid a cti o n of o n pla ti nu m a llo ys

,

u sed in p a r ti ng

Ni t t o-hydro chl o ri c a cid a cti on of o n pla tinu m

,

O x ida t io n
m et a ls, se q uence o f
O x idi zi ng po w er of a n o r e

Pa lla diu m beha vi or of d u ring a ssa y

,

d
eff ect Of a cid s o n

Pa r ting
p reca ut ions uri ng
r a t i o of go ld t o si lv er necessa r y

st rengt h Of a cids u sed in

 I ND E X

meth od for in gol d b ullion

prepa ra tion Of proof
r eta i ned b y pa rted go l d

d
w ei gh t a n V ol u me Of
S la gs assa y
,

cal cul a t i o n of

colo r Of

forma ti on tempera t ure of

na t u r e of
a ssa y of

s ili ca te degree of
S o d a a rgol met ho d fo r lea d o res
-

S odi um b i ca r b o na te
ca r b o na te
i
infl uence of o n red u ction of l t ha r ge
melti ng-po i nt of
ch lo r ide

c ya ni de

sulp h a t e f o r ma t i o n o f in a ssa y
,

S p r o ut i ng of sil ver bea d s

S ulphi d es a ssa y of
,

r a p id meth o d f o r

red u ci ng p o w er o f

S ulp h ur i c a cid a cti o n of o n p la ti num a l lo ys

,

S u r ch a r g e
S urf usi on of sil ver d u ring cu pella ti on

Telluride o res, losses in a ssa y Of

m et h o d of a ssa y o f
c o m p lex

Telluri um , c fiect of, o n a ssa y

el imina tion of d ur ing cu pella t io
n fica t io n
sco ri

qua ntit y Of in o res ,

Tem pera t ure colo r sca le

Test lea d
T in o r es a ssa y of
,

i na ccu r a cies in .

cya nid e a ssa y f o r

G er ma n meth o d of a ssa y fo r
r esu lt s Ob t a i ned fro m

To ngs
m ult i p le fo r sco rifiers

U m pi r e a ssa y
 I ND E X 219

Weigh ing
er r o rs in
Weight s , a ssay t o n system
co nversi o n ta b le f o r

f or a ssa yi ng
mi lli eme syst em of
pla t inum
Ii d er

st a nd a r di zed

Z inc beha vio r of in a ssa y

, ,

Z inciferou s o res a ssa y of

,

cr u cib le m et h o d fo r

losses in a ssa y of