APR8 1 63

oI
nbureau of mines
report of investigations
6202

INFRARED STUDIES OF OLEIC ACID

AND SODIUM OLEATE ADSORPI'ION
ON FLUORITE, BARITE, AND CALCITE

By A. S. Peck

UNITED STATES DEPARTMENT OF THE INTERIOR

BUREAU OF MINES

1963
 INFRARED STUDIES OF OLEIC ACID
AND SODIUM OLEATE ADSORPTION
ON FLUORITE, BARITE, AND CALCITE

By A. S. Peck

... ... ... ... ... ... ... ... ... ... ... report of investigations 6202

UNITED STATES DEPARTMENT OF THE INTERIOR

Stewart L. U daH, Secretary

BUREAU OF MINES
Marling J. Ankeny, Director

The work upon which this report is based was done under a cooperative agreement between the Bureau of Mines,
U.S. Dep artment of the Interior, and the University of Utah.
This publication has been cataloged as follows:

P ec k, Alan S
Infrared studies of oleic acid and soditun oleate adsorption
on fluorite, barite, and calcite. [Washington] U. S. Dept of
the Interior, Bureau of Mines [1963]

16 p. illus. 27 cm, (U. S. Bureau of Mines. Report of investi-

gation s, 6202)
Bibl iography: p . 16
3ased on work done in cooperation with the Univer s it y of Utah"
1. Oleic acid. 2. Sodium oleate. 3. Spectrum, Infra-red. 4.
Adsorption. I. Title. (Series)

TN23.U7 no. 6202 622.06173

U. S. Dept. of the Int. Library

 :::ONTEdTS

Sunnnary •••••••••••• ...................................................... 1

Introduct ion ••••••• ...................................................... 2
Acknowledgments •• •••••••••••••••••••••••••••••••••••••••••••••••••••••••• 2
Ma terials and exp e rimental p roc edur es • • • •••••• • •••••••••••••••••••••• • ••• 3
Infrared procedures ••••••••••••• • •••••••• • •••••••••••••••••••••• • • • • 3
Materia ls and their preparation •••••••••••••••••••••••••••• • •• • ••••• 4
Experimental procedures, • ••••••••••••••••••••••••••••••••• • •• • ••••• ~

I nterpretation and correla t ion of experimental results • •• •••••••• • • • ••••• 5

Infrared spectra of mine:c als and of collector compounds ••••••••••••• 5
I n frared spectra of reaction products occurring in a water system ••• 7

..........................
Infrared spectra of reaction products occurring in a nonaqueous
system •• ••• • • • • 12
Di scussion of results . ............ .... ...... . 15
Bib liogr aphy 0 •• • • • •••• ..... ............. ..... ......... ..... .......... . 16

Il..LUSTRATIOF

Fig .

1. Infrared spectra of fluorite, barite, and calcite • •••••••• ••• ••• • • • 6

2. Infrared spectra of oleic acid and so dlum oleate ••••••• • •••• • ••• • • • 7
3. Infrared spectra of ca lcium and barium oleate • • •••• • ••••••••• 8
4. Infrared spectra of fluorite with adsorbed collector from
aqueous solution • ••••••• • • • ••••• • ••••••••• • •••••••••• 9
5. Absorbance as a func tion of soncentration of collector . 10
6. Adsorption of oleates on fluorite as a function of pH • ••••• • •••• 1l
7. Infrared spe~tra of ~hemisorbed ol ea te on bart t e and calcite •• • • 12
8- Inf r ared spect ra of oleic acid mulls of fluorlte and barite • •••• • • • 13
9. Infrared spectra of gas evolved from rea ction of calcite with
o l eic acid ••••••••••••••••••••••••••••••••••••••••••• • ••••••• • •• II 14
10 . A mechanism for c hemisorption of oleic acid on minerals •••••••••••• 14
 INFRARED STUDI ES OF OLEIC ACID AN D SODIUM OL EATE
ADSORP TION ON FL UORI TE, BAR IT E, AND CALCITE 1

by

A. S. Peck 2

SUMMARY

This report presents the results of a cooperative study between the

Bureau of Mines and the University of Utah to define the mechanism involved in
the adsorption of oleic acid and sodium oleate on fluorite , ca l cite , and
barite, using an infra~ed spect r ophotometer fo r identifying and measuring the
adsorbed reagents and reaction products,

Fluorite.; calcite, and bar i te react \Vlth oleic acid and sodium oleate in
a water system, forming chemisorbed and solution products. The ch'";misorbed
species is a surface mineral cation - c o~lector anion salt, Chemical ana l ysis
of solution resulting from the adsorption rea ction i ndicates that the adsorp -
tion process causes disp lac2ment of minera 1 an i ons , namely , flu o r ide , ca r bon·
ate , and sulfate from the surface of these minera ls.

Infrared ana:ys~s of mineral surfaces of f l uor it e and cal c ite contacted

wi t h oleic acid in the absence of wat e r reveals that the co lle c tor r eacts wi1::h
both minerals. Fluorine and c a rbon dioxi de are r e leased by dec omposit i on of
fluoride and carbonate , respec tiv e ly , when these r e act i ons occu r . In the
absenc e of water , barite and oleic acid d o no t react .

Adsorption by the th~ee min e rals of e xcess c o lle c tor i n t he form o f

sodium oleate or o l eic ac~d occurs under certa in c onditions . At pH va l u e s
below 8 . 0, multi l ayer adsorption of oleic acid a nd an a ssoc iativ e decrea s e in
c hemis o rption occurs . Th e c ol l ector i s pr esent almos t e nt i r e ly in the c h emi·
sor bed form at pH values b etwe en 8 and 10 . At p H v a l u es a bove 9 . 5 th ere is
evidence of the p r esence of so di um o l eat e on the mi n e r al sur fa c es , pr obably
i n the form of mice l les .

The results pertain~ng to adsor p tion of ol e i c a ci d from aqu e ous solution

are inconclusive when det e rm i ning wh eth er or not the adsor p t ion proce ss is
based on a neutral molecul e mechanism or ion e x c hang e, s i nce neutral - molecule-
exc hange adsorption also would r esu l t in disp l a c ing of anions f r om th e mineral

lWork on manu script completed August 1962 .

2 Ex tra c tive metallurgis t, Salt L~ke 8ity Metallurgy Re sea rch Center , Bureau of
Min e s, Sa It Lake City , Utah_
 2

surfa c es . H01;vever , d ir ect con ta ct of the minera l wi th oleic acid, as was car -
ried o u t in the oleic acid mull studi es with calcite and fluorite , resu:_ted i n
th e formation of the chemisorbed mineral cation - co ll ector anion species on the
surface by a neutra l molecule mechanism .

INTRODUCTION

Limi ta tions in methods of studying r eact ions at th e soli d- liquid inter-

face have r esulted in the pr opo unding of marty f lo ta ti on theories during t~e
past 30 years . A chemical theor y of fl o tation desc r ibed b y Taggar t (11)3
involves the r e ac:: i on of oxidi z e d layers o n mineral surfaces with collector
ions i n aqueous so luti on . Wa rk a nd Sutherl and (11) a n d Gaudin (2) explaLned
col lect or adsorption ac c o rding to an ion - exc h ange mod el , where collector ions
e xch ange with ions adsor bed on the solid su r fac e . A mo re recent theory of
co llector adsorption de scribed as a neutral - molecul e theory was proposed by
Cook (1) and advanced in 1950 t hrough the e xp eriment a l work o f Hamilton,
Johns , and Bra d for d (2) on sev era l fluor i t e or es , using oleic acid as a
c ol lec tor .

Recently , infrared spectroscopy ha s be en applied as a means of dir e ct

study of a ds orb a t es on surf a ces . Eyr in g and Wa d s wo r th (~) obtained differen-
tial infrared spectra of so l u tion a n d vapor phas e adsorption of hexanethiol on
sphale r ite and z inc ite , i nd i c ating that water was split from the surface Sit2S
when the mercaptan was ads orb ed . The presence of ammonia and ammonium ion on
the surface of a 2racking catalyst has bee~ reported by Mapes and Eischens (11).
Duval and LeComte (3 , 4 ) have empl oyed i~frared methods for studying the degree
of polymeri z ati on of molecul es and for fOllowing reactions in the solid state .
An excellen t review of infrared studLes of surface··adsorbed molecL.lues is
given by Eisch ens and Pliskin (2).

It was believed that the appli c ation of infrared techniques would con -
tribut e to an understanding of th e nature of aQSOrptlon in fatty - acid flota -
tion. Hence, the adsorption of oleic acid on the surfaces of the three com-
monly associa t ed min2rals , fluorite , ba rit e , and calcite. was studied by means
of i nfrared spectropho t ometry .

ACKNOWLEDGMENTS

This inves tigation was sponsored through a cooperative research fellow-

ship agreement betveen the Bur-eau of Mines and the University of Utah.

'Lhe research proposal ,vas suggested by Dr. 1'1" E. Wadsworth, Head, Depart-
ment: of Netallurgy, University of Utah, who directed the study; and Dr. }L A.
Cook, Director of the Inst it ute of Metals and Explosives Research, University
of Utah e

'3"Jnderlined numbers in parentheses refer to items in the bibliography at the

end of this report. Page references refer to pages in the items and not
in this report.
 3

MATERIALS AND EXPERIMENTAL PROCEDURES

Infrared spectrophotometry comprised the principal method for studying

the surface reactions of fluorite, calcite; and barite with oleic acid and
sodium oleate, The infrared techniques employed, the methods used in prepar ..
ing the test materials, and the experimental procedures utilized in conducting
the research are discussed separately.

Infrared Procedures

Infrared spectra covering a wavelength range from 2 to 15 microns were

recorded on a Beckman Model IR- 44 double - beam i nfrared spectrophotometer,
using a sodium chloride prism. The amount of sample placed in the infrared
beam depended both upon the technique used and the relative absorption coeffi-
cients of the sample within the wavelength span covered.

Three methods were used in studying compounds by infrared spectrophoto-

metry. A KEr pellet technique described by Kirkland (10) was used to identify
solid compounds and quantitatively measure oleic acid, sodium oleate, and
chemisorbed calcium oleate. The second method of analysis employed was an
oleic acid mull technique similar to the Nujo l mull method (1) . The third
method employed a gas absorption cell with sodium chloride windows for analyz·
~ng gas evolved as a result of dry-state reactions.

Samples for infrared study by the pellet method were carefully weighed,
added to 1 gram of infrared'-grade of potassium bromide, and ground to a fine
powder in an agate mo r tar . This powder then was added to a plastic vial and
agitated for I minute in a vibrator mixer . A weighed amount (400 milligrams)
of the mixture was transferred to a die , evacuated for 5 mi nutes , and pressed
for 1 minute at 55 tons per square inch pres s ure . The resulting pressed disk
was used as a window pellet to determine the infrared spectrum of the material
suspended in t h e KE r matrix. Pe l l e ts \Vere stored in an indivldual envelope,
in a desiccator , when not in use . Each pellet was approximately I 2 centi·
meters in diameter and 0"2 centimeter thick o

Quantitative analyses were based on the measurement of the infrared

absorption intens i ti e s of prominent and c ha r acteristic bands of the compounds
at specific wavel e ngths by the tangent baseline method Infrared absorption
intens i ties were measured for the c arbon y l stretching modes for ole~c acid,
so d ium oleate, and sur~ace calcium oleate at 5 . 8 2 - , 6 . 40 - , and 6 . 43 - mi cron
wavelengths, resrectively Plots of the concentration of standard samples in
KEr, aga in st the absorbance , were made to ob ta in working curves used in calcu
lating the concentration of adsorbed collector on fluorite .

Quant i tative measurements of the oleic acid and c h emisorbed calcium

Gleate on mineral p articles were obtained direc tly f r om spe c tra of the mi~eral
surfa c e . In tests c onducted above a pH of 9 . 0 , the amount of sodium oleate

4 Reference to t r ade names is made to facilitate understanding and does not

imply e ndorsement of such brands by the Bureau of Mines
 4

adsorbed on mineral surfaces was determined b y washing the mineral part~c12s

with distilled water, evap o rat i ng th2 water , and analyzir:g the res5.due for
sodium oleate .

Diff2L'ential spectra of the potassium bromide sample pel12ts Here

obtained by placing standard pel:ets containing only the mineral in the refer~
ence beam of the spect r opho t ome ter. Th i s procedur e provided spectra of only
the surface compouncis of t he sample, as all other spectra ,vere canceled
rhrougt th~ do u b l e - beam o p t i cs of the instrument .

Ma t er i als and Th e i r Pr epa r a t i on

The minerals used for i nf r ared study in this investigation were hand·
selected from miner a l ogical s pecimens . Chemi cal ana l ysis fa i led to indicate
the presence of wa t er - soluble salts . Fluor i te and calcite crystals were 98
p e rc ent p ur e . The b a r it e was 90 p er c en t p u re , con ta i n i ng numerou s eX':'caneous
metal l i c elements; stron tium ,,,,as the p r inc i pal impurity

Mineral pa r t i c l es for infrare d s t udy were obtained by grind ing approxi-

mately 100 grams of crushed min e ral crystals fo::: 8 hours in a FisheL' gr:'nder
A sus p ension was mad e by mi x i ng t he powder obtained ,,,ith 2 liters of distilled
water . The upper half of the sus p ens i on was decanted after 1 tour of settling
and used as a standard for exper i men t al determinat i ons. riineral suspen s ions
containing about 2 grams of mine ral per liter we r e ma1e by ':his method for
each mineral studied . Dry po,,,,der use d for surface studies was obtained by
centrifuging the colloidal suspension and drying the obtalned solid mat e rial
In an oven at 40° C. Mineral particles obtained through the foregoing proce -
dures had an average particle size of less than 0 .15 micron as determined b y
electron microscopy . Th e small particle size minimized scattered infrared
radiation and prov i ded la r ge surface areas for adsorption r eaction and subse-
que~t infrared absorption measurements .

Calcium carbonate and calcium fluoride of U.S,P . reagent - grade qual~ty

were used for oleic ac i d adsorpt~on tests carried out in the absence of water
The spectrum of oleic acid ',las obtained from u.S.P, reagent 'grade oleic acid,
and spectra of calcium oleate and sodium oleate ,·'ere obtained from chemicals
of 95 to 99 percent purity; the principal impurity was oleic acid. Barium
oleate was prepared in the laboratory by filtering the precipitate from barium
chloride-sodium o~_eate so l utions .

Ex per i mental Procedures

Collector adsorption reactions were obtained by adding 1.0 milliliter of

0.,01 molar sodium oleate to 20 cubic centimeters of mineral suspension, while
the latter was agitated at a stirring speed of 1,520 revolutions per minute,
Hydrochloric acid and sodium hydroxide were used for pH control. Each
adsorption reaction was allowed to continue for 2 hours, then the solids in
the suspensio~ were filtered out, Calcium chloride was added to the filtrates
to precipitate the mineral anions for analysis and identification.
 5

Oleic acid·mineral mul l s were pr e p ared by mix i n g 2 d rop s of ole i c a c i d

with 100 milli grams of dry powde red miner al c onta i n ed on a silver chl o ride
window . The material was smooth e d out wi th a s pa tu la t o a fine f i lm on the
window and placed in the sample beam of t he s pect r ome ter fo r analys i s . The
spectra were compaled ,,,ith thos e of r eference samp le s of ( 1) p u re oleic a cid
and (2 ) the mineral Lnvestigated.

The followex"g proc:=dure for gas a na l yses was used i n the minera l-
collec tor ad sorption tests . Min e r al powder (200 grams) was a dd e d to o l eic
acid ( 200 millili:::ers ) contained in a I - liter po ly ethylene b o ttle . The b ott l e
containing the reactants was tigh t ly stopp e red and g ently agi t a ted . An evacu-
a ted sodium chloride gas absorption ce l l ,,,as u s e d to wi t hdr aw part of th e gas
present in the bottle. The ce l l then was plac ed i n th e sample beam of the
iEfrarej spectrophotometer and the presence o r absence of vapor reac tion pro d-
ucts was determined .

INTERPRETATION AND CORRELATION OF EX PERIMENTAL RESULTS

The e x per imenta l results we r e interpret ed on the b asis of corre la tions

and compar i sons of the infrared st ructur es of th e mi n e rals and collector
r eagents with those of the films formed on the min eral s aft e r contact with
the collector . Evaluation of th e positions and amplit udes of t he cha racter -
istic infrared bands of the different organic a n d i norganic c ompounds invo l v ed
in the reactions permitted direct qual itative and quanti t a tive d efinition of
the character of the adsorbed species .

Infrared Spectra of Mi n e rals and of Coll e c t or Comp ounds

Infrared absorrt1on spectra of the three nonmetallic minerals, f l uorite ,

barite, and cal cite, are shown in figure 1. The s p ectrum o f fluorite shows
only hydroxyl bands associated with surfaces at 2 .9 and 6 . 1 mic r ons , corre-
sp onding t o O- H stretching and bending , respectiv e ly . The a bs e nce o f inter -
fering inf ra red bands in fluorite makes it an ideal mineral for infrared sur-
face studies . Barite and calcit e show the many c ha ra c ter i stic bands of
sulfates and carbonates, respectively, both exhibi t ing strong absorption in
the intermediate frequency region.

The infra r ed spectra of oleic acid and sodium o l eate are shown in figur e
2. The band at 5 . 82 microns for oleic acid r esults from the ca r bonyl c=o
stretching mode and is characteristic of c=o when assoc iated with the acid
carboxyl group, COOH . Ionization of the ca rboxyl gr o up to - COO - shiftsi:he
associated C=O band to h igher vlav e lengths . The strong bands at 6 .40 microns
and 6.8 to 7. 0 microns for so d ium olea te repres ent the a ntisymmetrical and
symmetrical vibrations , resp ectiv ely , of the ionized c arbox yl group . The CH3
and ~ stretching frequencies for o l eic acid and sodium ol ea te occur at 3 . 37
microns , with a separate CH3 band a t 3 . 52 microns . The additional bands for
oleic acid i n the regi on 3 to 4 mi crons are OH stretc hin g bonds of s trongly
hydrogen - bon de d a cid d imers . Fr e quen cy assignmen ts fo r o l e ic a c id in th e
intermediate wavelength region a re ~ deformati on mod e s at 6 . 83 mic rons and
C- O stretching modes from 7- to l a - micron wavelengths . The broad band a t 10. 7
microns fo r olei c acid corresponds to an OH out - of -p lane deformatlon group.
o

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FREQUENCY, cm.-'
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FIGURE 1. - Infrared Spectra of Fluorite, Barite, and Calcite.

 7

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WAVELENGTH, microns

FIGURE 2.• Infra red Spectra of Oleic Acid and So dium Oleate.

The band at 13 . 8 microns is caused by ( C~)4 skeletal v i brations . Sodium

oleate shows two weak skeletal vibration frequencies at 13 . 8 and 14 . 3 microns ,

Figure 3 shows infrar2~ spect r a for calcium oleate and barium olea te
b:lth water -insoluble salts of ol e ic acid. The carbonyl antisynnnetrical
stretching group for calcium ol eate shows two highly reso l ved bands a t 6 . 34
and 6 . 48 microns , which a r e at lower wavelengths than th e band fo r the carre·
sponding carbonyl group for barium o l eate at 6 . 6 micr ons .

Infra r ed Spectra of Rea ct ion Products Oc curring i n a Wat er Sy st em

SFectra of collector films a d sorbed on fluo ri te from sod i um oleate solu-

tions ar~ shown in figure 4 . Carbonyl groups may b e seen a t 5. 82 and 6 . 43
microns for collector adsorption at pH 5 . 5 . The band at 5. 82 microns c orre -
sponds to the character i stic carbonyl frequ ency of ole i c a cid , but t he band at
6 . 43 is new. The 6 . 43- micron band represents a s ur f ac e c ompound of calcium
oleate having sl~ghtly different spectr a than tha t of bu l k calc i um oleate
 FREQUENCY, cm.-'
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(f)
CD f - , ~
<! f-~~-+-- r----r--+--r--r~r--~~'-+--+-r--r-r--'+- CALCIU M OLEATE
..
.6 r-- .;'\

r- I 0 . 1 pe r c e nt in KBr
.8 f---
10 f=::=
15 _ / i 1
=:-f=.==t-_-
ro '==2 '
3 4 5 6 7
WAVELENGTH , microns

FREQUENCY, em:'
o 5000400030002500 2000 1800 1600 1400 1200 1000950900 850 800 750 700
,;;;..rr'"
)/~
- - j
i ' 0F
!
... 1

""'"f\-
_. . -

--- '- . - ( .- -- - - - -
r-: -

~ -r -.I-

~ ~~
I
/V .. -- _. --_ . - - -- ---
w .2
/ 1 ' ..- f--, -- i
~~
u
z
<!
CD
----
/ ! - 1·-- -- - - -~ f--

Q: I i
0 1 --
/"\
(f)
CD
.4 , -I --- - - -- f-- o -
<! 1\ BARIU,'v1 OLEATE -
6.60 ~ ---- -

~t=-
.6 / ~

0 .2 per c ent In K B r
-
8
1.0 -
.. - '
,- -
-
- -
'--
'---
---,
--I l-
,
=-=L-.l=l-=: _-
-
,- ,--riO
]
1.00
5
2 3
-4 5
--
6 7 8 9 10
-_L
II
l __ f~1
12 13 14 15
WAVELENGTH, microns

FIGURE 3. - Infrared Spectra of Ca lcium and Ba rium Oleate,

shown in figure 3 . The sp ec t rum of f l uorite with adsorbed cOLlector from solu'
tion above a pH of 12 . 0 sh ows a carbonyl band with maximum a bsorption at 6.40
microns . This band at 6 . 40 microns was attributed to the formation of sodium
oleate micelles at the mineral surface, as would be expected if sod1um oleate
were a d sorbed physically at high pH values . Also, variations in the absorp"'
tion intensi t y of d i fferent pa:.:.·ts of the carbony l groups were evident with pH
changes , for examp l e , the infrared absorbance at 6.2 - and 7. 0-micron
wavelengths .

Infrared s p ectra of fluorite from all adsor ption reactions showed only
the characteristic a bsorption spectrum of chemisorbed calcium oleate after
washing w1th alcohol or water . Physically adsorbed films of oleic acid and
sodium oleate were removed easily from the mineral surfaces, resulting in the
disappearance of their superimposed absorption spectrum. The speccrum of
sodium oleate when superimposed on the spectrum of the chemisorbed oleate
obscured the band at 6 . 43 microns . The band at 6.43 microns is characteristic
of the oleate chemically bonned to the mineral and is the only band in
 9

FREQUENCY, em."

_.
5000 4 000 3000 Z~OO
- _. -- .-- '
ZOOO 180 0 1600 1400 1200

v
t'"
V- --
1000 950 900 850 800
r--.. ~
750

I
700

--.
I , r\
I V-- _..
: \..V
u.; .2
--
/"\ II
- - - -' -- . --- ~ - .-
- . .. -

u
/ r
.z.:;:
m
0:: /
/ V
, •
-t--'- .- .- ."

"
_.--
..
-

-- - . - - -
o r; ;'
If)
.L "'--
m - -- '-'

« -- I "'---HYd r Ogen bonded dimer pH 5.5 ADSORPTION -

I'
-
2.0 "arcent in KBr -
f--
f- f- .
I. r--
I. 5
1

2
Y Y

3
,

4 5 6 7 8
--
9 10
I
II
I I
12
1- f
13
" L. I
14
I -
15
WAVELE NGTH , microns

FREQUENCY, em.-'
2~00 1800 !.§.Q,0[!"J1g \2rr 'l ,~ ~p p,.~ Iq009 50 ~ 00 850
.7~
5000 4000 30002500 800 75C
o . , -1. --., . ' I'
f- - 1-;-"" --- V:...--
-

V
Ir-
'"'-.---

w
u .2
z _.--
---

.
,
- V
k:::~_
V 1\
\
n V I
---

-- f- --
- .. -. -. - .- . _L

- --
« / _ .
.

CD f--
0::
0
.- -- If
If)
A pH 5.5 ADSORPTION
-
(JJ
. -'r.. .. .
« 6.43 fl-.---'"" -
1,1 : II Alcohol wa sll
.6 .\ ~- 1-
2.0 percent In KBr
I-
.
r--
.8 -- .
1.0 , -- ,. -.
: .5
a>
-
--
I --. I I I I -. I I .l --I·--::--:
2 3 4 5 6 7 98 10 II 12 I~ 14 15
WAVE L ENGTH, microns

FREQUE NCY, em.-'

o 50004000 3000 2500 2000 1800 1600 1400 1200 1000950900 850 800 750 100
~ !~ 4± 'T:I~ '-
~.-- ; I ~ -'--
Ir'! i:: :,

~ 2M ,. . .:. -. _ /V -- -
m " 'V
g;
If)
~r---~-
. 4 &j~
: ~-4-4--+-~-+-~~-4~n--+-+--+- ·~--r~-~
/
~ T;c-" -- -- --. ---/
pH 12 .0 ADSORPTION
1L--t--4- t---ttf-1r-+-
.6r.I.:.. 1
--+>-'-+--1--1-
I--- - - -- I--- r--
2.0 percent in :(B ..
I---+--'-J-+----jjf--+---+- 6 .4 0 fl- --- -+----j--j--. - - - +-- 1-+----+-- ~-

.8 ----r- ,-
j-'-:
:~b~-~2~./dV"'v
==;!c==L .=..,~=+=='===;l_J=='~~-=±
6 7 3
I' =k=.~'~·.L~b~~~-~~--J~.
II 4 5 8 9 10
L J12 L I
13
W~ '==i
14 15
WAV EL ENGTH, micro ns

FIGURE 4. - Infrar ed Spec tra of Fluorite Wi th Adsor bed Col lector From Aqueous Solution .
 10

0.6,---------,----------,----------,---------,----------,---------, evidenc e in the

6.4- to 6.5-micron
region for adsorp-
tion at pH values
less than 8.5 •
.5
Figure 5 shows the
quantitative rela-
tionsh i p between
the percentage of
.4 concent r ation of

w
• collector in its
various forms in
u ()
z 400 mg of potas-
«
CD sium bromide and
0::
0 3 the intensity of
(j)
CD the carbonyl
«
stretching fre'"
quencies . The
2
Beer - Lambert Law
(~) was obeyeci for
the concentratlons
used .

.1 • o Oleic acid, 5.82 microns Figure 6

• Sodium oleat e , 6.40 microns shows the influ -
() Chemisorbed calciutTl oleate, 6.·:f3 microns
ence of pH on the
surfac e concentra -
tion of oleic acid ,
o O.O~ 0.06 0.08 0.10 chemisorbed ca l c i um
COLLECTOR, percent in 400 mg. KBr oleate, and weakly
bonded sodium
oleate on fluo~ite.
FIG UR E 5. - Abso rbance as a F unc t ion of C oncentrati on of Co l lectoi.
The optimum range
fer chemisorption ,
as indicated by the presence of calcium oleate, was between a pH of 8 and 10 .
Only minor amounts of physicaliy adsorbed oleic acid or sodium oleate Dere
observed in this range . The maximum 0: the chemisorbed oleate near 58 mg pe r
g r am of mineral would require a particle size in the range observable by the
electron microscope . At pH values below 600, ole i c acid agglomerated in multi -
layers on the mineral particles, and acid dimers were identified in the 3- to
4 - micron region of the infrared spectrum as shown at 3,.7 microns in figure 4 ..
Regions of excess physically adsorbed oleic acid coj_ncide with pH values ""here
flotation is notably poor (1) .

Fluoride ions displaced from the mineral surfaces to the solution during
chemisorption were identif~ed quantitatively by gravimetric chemical analys i s
of the calcium fluoride prec~pitated by adding c a lcium chloride to the solu-
tion" An equivalent stoichiometric amount of fluoride ,vas replaced by the
chemisorbed oleate.
 11

6 0 , - - - - - - - - , - - - - - - - , , - - - - - - - , -- -- - - - - , - - - - - - - - , - - - - - - - - , - - - - - - - - ,
The differen-
tial spectra of
\ figure 7 represent

\ •
collector adsorp-
tion of oleate
•
50-
\ from solution on
calcite and barite .

\ For calcite the

deep carbonyl band
., 0\ near 6,3 microns
indicates collec-
~
a 40
\ tor chemisorption.
Also, chemisorption
'0

~
0'
E \ is indicated by
increased inten-
~
sity of the band
Cl.
30 o Physically adsorbed oleic acid in the region of
'"E • Chemisorbed oleate
Q Physically adsorbed sodium oleale
3.5 microns
~
0'
because of the
=E superimposition of
o- the CHs and c:~
W
m 20 bands on the ~eak
0::
0
U1
carbonate struc-
0
« tur 2 in this
W
region. The exact
f-
<l position of the
w
-' carbonyl band is
0 10
uncertaln becaus e
the spec t rophoto-
meter was ~nsensi­
tive above 6 . 3
microns , owing to
the highly inter -
fering ca rbonate
pH
i nfrared absorp -
t i on band . Carbon-
FIG URE 6. - Adsorpt io n of Olea te s on Fl uori te as a F un cti on of pH. ate ions we re i den -
t i fied in solution
a s a result of surf a ce r e a c tions of calc ite with coll ec tor in water . The ter-
minal pH of ,:a lcite solution r eactions was 10 .5, compared with a pH of 7 . 5 f or
fluor i te reactions . This hi gh pH for ca l cite rea ction s was fu r ther evidence
of the exc hange - adsorp t ion proc e ss between th e collec tor and the mlneral sur -
face carbonates . Figure 7 a lso shows ch emisorbed oleate on barite as a result
of collector - minera l interactions in water . The antisyrnrnetrical ,:: arbonyl
group appears at 6.48 microns compared ,.;r ith 6 . 60 microns for the corresponding
carbonyl band for barium oleate shown in figure 3 . Sulfates appeared in solu-
tion af t er adsorption and we re identified by precipitation technique s.
 12

f---h---t--Hrtt---j- - ---

CALCITE

Differential spectra
Sample ' I 0 percent in KBr
Ref~rence ' 0 . 75 percent in KBr , I
-'-- '

4 5 6 7 8
- LI---+d~~~_
9 10 II 12
, ~_ +o-J.~_4L=_~_l-1~==-lj~-LJ
-,1I"--
13 14 '--' 15
WAVELE N G T H. mic r ans

FIGURE 7. - Infrared Spec tra of Chemisorbed Ole(1ta on Ba rit e and Ca lcite.

Inf r a r ed Spec t ra of Reac t i on Products

Occu rring in a Nonaqu eou s System

Dir ect cont act of dry f luor i t e wi th ole ic ac id r esulted in spontaneous

chemisorp t i on, as shown in t h e f luori te s pectr um of figure 8 . The band a t
6.43 mi cr on s c o incides with the c a rb ony l s pectr um of oleate chemisor bed on
fluo ri te fr om aqu eou s s olution. Simi l arly, chemis orbed f ilms of oleate on
c alcit e were obs erved nea r 6.3 microns f or nona que ous con tact of th e minera l
with ol eic a cid. The formation of a mineral cation-collec t or anion species on
t he surfac es of fluorite and calcite r equired t h e di sp l ac ement of anion s fr om
the minerals to cons erve electrical neutrali ty . Also , t h e hydr ogen di s p laced
f r om ole ic acid during chemisorption was expect ed to combine with t he miner al
anion s a nd f orm hydrofluoric and carbon ic a cid, resp ec tive ly . Thu s , infrared
analysis was made of the v apor phase to determine if hydr ogen fl uoride and
carbon d i oxide, a decomposition product of c a r bonic acid , were pr esent .
 13

w
u
z
.2
-
1'\/ '\
~
-
<l:
III • . I
a::
~ r--
0 --
en .4
III .--
<l:
,If I
.6
.8
1.0 ·1
1.5 - - - -

"" 2
WAVELENGTH, microns

FREQUENCY, cm.~
o 50004000 3000 2500 20001800 1600 1400 1200 1000950900 850 800 750 170.0,.,-.,.-,
,Il '1' 1' 'I" " ]"" '1''''' [ '' I' r
~. ,;:-~ .~r-----
I

:.'-:.: ~. I /\~,-

r
11:1 ; /\ 1\ BARITE
w ~- .-- 'No 1\ AgCI window r V

F+l±"~ft-~,--:-+H-'~- ,-t---,~:, --+1+-/I~f- - 1I +- ·

+--. --++---I--+-t-+---+-+--+--+-+---+--+--+---+l--
i --+\t---+-- ( V ~ 1-
~ .4 ~1;"'-- -Li- - - - - / \
~.~~!~
,6 " L
I<~~~~
'., ,I
; -'I~.H~~1--+~~+1~~~~+-~-+~~+--H/
I II L+~~\~A--+~~+--t
r '-­

.8~f';'~:·~F~~~I"~
' ~~;f~Fflt=f~~t~~F~~~$==f-~·-fF~~·-~F~~~f~~F -'--
::~ ~Ii~: ~~
2 3 4 5 6
'\I
7 8
1\
9 10
I
II 12
L
13
'J,:1:
14 15
WAVELENGTH, microns

FIGU RE 8. - Infrared Spectra of Oleic Acid Mu l ls of Fluori te and Ba ri te.

The gas s pectr a recorded for vapors evolved dur i ng dry - state reactions of
oleic aci d wi t h calcite sh owed c onsiderable c arbon d ioxide and vapor phase
ole ic ac i d, as shown i n figure 9. The bands at 2 . 7 , 2. 8 , 4 . 2, and 13 .9
micr o"·. s are c harac t eristic carbon di oxide vib r ational mod es. The character -
is t ic infrared abs orpti on of liquid and vapor ole i c ac i d are shown in f i gures
2 and 9, r es p ectively , and reveal fundamental dif fere nce s in the molecu l ar
v i bra t ion of t he ac i d i n these two different states .

The absorpt ion spectrum of v ap or evolved during dry- s t ate r eactions of

fluorit e wi th o l eic ac id showed only characterist ic spect r a of vapor-phase
ole ic acid and trace amounts of carbon diox i de a tt r ibuted to the decompos i t i on
of small amounts of surface- adsorbed c a r bonate on t he mineral . Hydrofluoric
ac id has a smal l absorp t ion coeff icient and was , theref ore , not expected to be
pr esent in sufficien t quantities for infrar ed detect i on . Further, hydr ogen
fluoride may be expected to rea::t with e}~cess o l eic acid i n the syst em and
wit h th e glass infrared gas cell .
 14

FREQUENCY, cm."'
o 5000400030002500 20001800 1600 1400 1200 1000 ~150 ~IOO 85C 800 75C 7'Oe
- 1-- .- .- .. -:~ ~~ ~--~~_ ,;... - -~ _~ ~,.;':.-~~_ .~~~ I

Vapo r contain e d in 10em.

NoCI li as absorption ce ll.

FI GURE 9. - Infrared Spectra of Gas Evolved From Reaction of Calcite With Oleic Ac id.

Oleic a c id

Minera l Free acid adsorpt i on Chem i sorp t ion

FIGURE 10. - A Mec hanism for Chemisorpti on of Oleic Ac id on Minerals.

Carbony l band s do no t a pp ear in the bar i t e mull s pectrum of f i gure 8,
indica t ing th a t ol e ic ac i d d oes n ot react wi th ba rite in the ab sence of wa ter.
Ha d c hemi s orption occurred, the barium oleat e carbony l band a t 6. 48 micr ons
wou l d hav e be en i n evi dence (fi g . 7 ). If chemi ca l rea c tion wer e t o oc cur in
 15

a nonaqueous system between oleic acid and barite, sulfuric acid--predicted as

a reaction product--would remain at the solid interface because of its
extremely low vapor pressure. The resulting high acid concentration at the
surface would reverse the reaction because chemisorption is suppressed in sys-
tems of high acid concentration. Thus, it is logical to assume that in solu-
tions with high pH, the acids formed at the surfaces are reIT~ved readily and
permit chemisorption to ensue. It should be noted, however, that this postu-
lation does not rule out the possibility that ~.;rater may act as a catalyst in
the barite-oleic acid adsorptive process.

DISCUSSION OF RESULTS

The reactions of fluorite, barite, and calcite with oleic acid or solu-
tions of sodium oleate result in tightly adhering collector-anion mineral-
cation mono layers. The infrared results did not enable a distinction between
a neutral molecule and ion exchange mechanism for the reactions occurring in
aqueous solution because three species of collector were present. These were
collector ions, neutral molecules of oleic acid formed by hydrolysis, and
neutral molecules of sodium oleate.

A nonionic mechanism was apparently required for the collector-mineral

interactions occurring in a nonaqueous system. The nonionic or neutral mole-
cule adsorption illustrated in figure 10 required (1) physical adsorption of
the fatty acid, (2) dissociation of the acid carboxyl group, (3) mineral-anion
displacement, (4) mineral-cation collector-anion molecular association, and
(5) the formation of a mineral acid. Based on the reasonable assumption that
the mode of collector-mineral interactions are the same in aqueous and non-
aqueous systems, oleic acid formed by hydrolysis of sodium oleate also is the
principal collector species involved in the reactions occurring in \Vater.
 16

BI BLIOGRAPHY5

1. BARNES , R. B., GORE, R. C., WI LLIAMS, E. F., LINSLEY , S. G., AND

PETERSON , E. M. I nf r a r ed Analysis of Crystalline Penicil l i ns . Anal.
Chern., v o l . 19, 1947, p . 620 .

2. COOK, M" A. Mechanism of Collector- Mineral Attachment and Development

of New FlotatiGD Te~hniques" Eng . Min . Jour . , vo l . 150 , 1949 , p . l~Or

3. l',JVAL C" AND ;:'eCOMTE_ J (Det'2Imina t i on of t he Degree of Po 1ymeri?;a~

~ion of 0etallic 0inera~ Salts by Means of the Spec tra of I~frared
Absorption' CompL rend,. a-::ad .. s ci. U. R. S. S. ( Paris), vo~, 232,1951,
p~ 2306,

4. _____ ( The Stu dy of Some Solid State Reactions by Means of Infrared

Absor p tion Spec tr a .) Comp t. r end . acad o sc i. U. R. S. S, ~ Faris ) , vol"
234 , 19 52, p . 2445 .

s· EISCHENS, R. P., AND PLI SKIN, W. A. Advances in Cata lysis . Academic

Press , Inc ., New York , N. Y., 19 58 , p . 1.

6. EYRING , E. M. , AND WADSWORTH , M. W. Dif fe rent~a1 Infrared Spectra of

Adsorbed Mono l ay ers - n- Hexan eth i ol on Zi~c Mi nera l s . Min . Eng. , voi.
8 , 1956 , p. 53 1.

7, GAUDI N, A. M. Flotation. McGraw- Hil l Book Co ., I nc ., New York, N.Y."

1957 , p . 360 .

8. GLASSTONE , S Tex tbook of Phys i cal Chemistry. D. Van Nostrand Co.,

I nc ., New York, N.Y., 1946 , p . 58 1.

9. HAMI LTON, J . H. , JOHNS , J . W., J R., AND BRADFORD , H. R. Deve l C'pment of

New Flotat i on Techni que s . Utah Eng . Exp. Sta . Bull ., vo l . 40; No. 47;
1950 , p . 1.

10 . KIRKLAND, J. J . Quant itat i v e Ap p li ca ti or of Po t ass ium Bromi de Disc

Tech nique in Inf r ar ed Spectr os copy . Anal . Chern. , vo l . 27 , 19 55 ,
p . 15 37 .

11 . MAPES , J. E. , AND EISCHENS , R. P. Infrared Spectra of Ammonia Cherni

s orb ed on Cr a cking Cata l ysts . J our . Phy s . Chem. , vol. 58 , 1954 ,
pp. 1059 -1062 .

12 . TAGGART , A. F. Handbook of Mineral Dtessing . J ohn Wi l ey and Sons , Inc .,

New York , N. Y. , 1945 , p . 12 - 04 .

13. WARK , J . W., AND SUTHERLAND, K. L. Pr i n c i p les of Fl ota t ion . Australian

:r::nsL din . Me t. , 1955 , p . 142 .

5Tit les enc l os ed i n pa r entheses ar e t r ans l a t ions f r om the language in which

th e i t em was publ i shed .
I N T . " B U . OF M I N ES . PGH • • P A ~ 5039