394 K . L.

SUTHERLASD

(5) CORBIN,s., ALEXANDER, AI., AXD EGLOFF,G.: J. Phys. Colloid Chem. 51, 528 (1947).
(6) CORBIK, S., ALEXANDER, hI., A N D EGLOFF, G.: Ind. Eng. Cheni. 39, 1147 (1947).
(7) EGLOFF,G. : Physical C o m t a n t s of Hydrocarbons, Reinhold Publishing Corporation,
Yew 1-ork: Vol. I. Paragins, Olejins, Acetylenes, and Other Aliphalic Hydrocarbons
(1939) ; T-01. 11. Cyclanes, C'yclcnes, C'yclynes, and Other Alicyclic Hydrocarbons
(1940); Vol. 111. Mononuclear Aromatic Hydroca&ons (1946) ; 1701. IV. Polynuclear
Aronialic Hydrocarbons (1947).
(8) EGLOFF,G., ASD K U D E RR.: , J. Phys. Cheni. 45, 836 (1941); 46, 296 (1942); I n d . Eng.
Cherii. 34,372 (1942).
(9) EGLOFF,G., ASD K G U E RR.: , J. I'liys. Chem. 46, 28 (1942).
(10) EGLOFF,G., SHERXIS, J., ASD DULL,R. B.:J. Phys. Chem. 44, 730 (1940).
(11) FRASCIS, A . W.:I n d . Eng. Chern. 33, 554 (1941); 35, 442 (1943); 36, 256 (1944).
(12) GLASGOK, A . R.,JR.,STREIFF, h. J . , . ~ S D ROSSINI,F . D.: J. Research S a d . Bur.
Standards 35,355 (1945).
(13) HUGGISS, 11.L.: J. din. Clieni. Sac. 63, 116 (1941).
(14) HUGGISS,AI. L.: J. h i i . Cheni. SOC.63, 916 (1941).
(15) IVANOVSKI-, L., ASD B R - ~ X C K EAR. ,T-.: Petroleum 5, KO.10, 169 (1942).
(16) KIKNEY, C. R.: I n d . Eng. Cheni. 32, 550 (1940).
(17) I~ISSEY, C. R.: Ind. Eng. Chern. 33, 791 (1941).
(18) RISSEY,C. R.: J. Ani. Cheni. h e . 60, 3032 (1935).
(19) KIXXEY, C . R.: ,J. Org. Chem. 6, 220 (1941).
(20) KLAGES, F.: Ber. 76, 7bS (1943).
(21) KURTZ, S.S., J R . , ASD LIPKIX,11. R.: Ind. Eng. Chem. 33, 779 (1941).
(22) KURTZ, S.S., ,JR,, A N D LIPKIN,AI. R.: J . Am. Chem. Soe. 63, 2158 (1941).
(23) MIBASHAN, -4.:Trans. Faraday Soc. 41, 374 (1945).
(24) T.LYI.ort, W.J . , I'IGXOCCO, J. 11.,ASD ROSSINI,F. D.: J. Research Natl. Bur. Stand-
ards 34, 413 (1945).
(25) WIESER, H . : J. Am. (:hem. SOC.69, 17 (1947).
(26) WIESER, IT. : Private communication (April 25, 1947).
(27) WILLINOHAM, C . B., TAYLOR, W. J., PIGNOCCO, J. M., AND ROSSINI,F. D.: J. Research
Natl. Bur. Standards 35, 219 (1945).

PHYSICAL CHEMISTRY OF FLOTATION. XI

KIYETICSOF THE FLoTa.rroN PROCESS

T i . I,. d U T H E R 1 , h S D
1)irzszon of Induotrial Cheinzsiry, Comnionweulth Council for Scientific and
Industrial Research, Melbourne, Australia
Received A u g u s t 27. 1947

I . ISTRODL7C'l'IOh-

To detrimiiie tlw tliroretical rate of flotation of mineral in a cell, it is neces-

sary t o make 1i.e of ;I Yimplified model of the -!.stem, nhich ignores unimportant
variables u-liile retaining e*sentinl teatiire-. Theories of air-mineral adhesion
are discussed and tlic directt enc~oiinterhypothesis is chosen for detailed investi-
gation. .lny fiiilure of the subsequent theory t o describe tlie kinetics of the proc-
ess is certainly due t o oversimplification of the encounter hypothesis and some
attempt is made to a the importance of the simplifications.
 K I S E T I C S O F THE FLOTATIO?; PROCESS 395

11. T H E O R I E S O F I I R - M I X E R A L ADHESIOS

‘I‘aggart (21) observed that gas is deposited on non-polar surfaces from solu-
tions supersaturated m-ith the gas. In the subaeration and agitation machines
there are regions of high pressure and lo^ pressure before and after the impeller
blade. These pressures produce super- and iinder-sntmittiori, respectively, of
the pulp. The air can then precipitate from the supei,satiirated liquid on the
particles of mineral? and it is postulated that all mineral ivhich floats has heen
buoyed t o the surface by air attached in this way. Taggart also observed that,
in one test at least, conditioned particles falling on stationary air 1)uhbles {lo not
adhere, and he therefore declares the encoiinter proceps inadequate. Despite
Taggart’s assertion that ’This idea (i.e., the encounter hypothesis) (\\-as) con-
ceived in ignorance and horn in litigation, ivas foaered 1)y selfish interest and,
unfortunately. n-as copied into some textbooks”, k g d a n o v nnd Filanol
obtain opposite results in similar tests. They piwent diiwt evidence I
matographic record for the collision theory. l’artirles \\-it11 i t hydropliobic
surface fell on a stationary air bubble. They xlheiwl. Iluhblc~rising n-ith a
speed of 18 cm. set.-' (about 0.09 cm. radius) collided ivith and adhered t o .ms-
pended mineral particles (about 0.0075 cm. iadiiis). ‘The time required for.
adhesion t o the bubble of suitably conditioncd miiirixl TVW h t i v w n 2 :md 10
millisec.
Gaudin (Ga) and earlier investigators po,qtulatcd :i diiwt encounter, leading
to adhesion between suqiended mineral and the rising h b b l e . Treating this
process theoretically Gaudin shon.ed that no encounter \vas possible Iietwen a
bubble and a mineral particle in an itleal fluid (comp:ire later). Further, he
stated that in some experiments he found that “it is very difficult t o cawe cours-
ing air bubbles to pick up n-ell-prepared mineral particles” ((j, 11. 92). Despite
these difficulties Gaudin considers that the theory is more plaiisihle than the gas-
precipitation hypothesis, which lie rriticizes on the grounds that ( 1 ) \-;iciiiim and
pressure near the impeller blades follon. so mpitlly that buhble gro\vth is not pos-
sible; (.2) it is not posihle for one bubhle to grow siniultaneoi
particles, yet heavily armored biibbles are c.ommon in s;nitable
precipitation theory must lead to equal rates of fiotation’ of small and large par-
ticles, n-hich is not so. The first objection i> not important, since supersaturated
pulp could be flung from the impeller arid the gron-th of the hubble coiild proceed
s l o ~ d yin pulp distant from agitation (see also page -109). The second and third
objections are sufficiently important to ivnrrant dismissal of the theory as the
major method b - n-hich mineral is attached to b ~ r b b k which
s biiog it t,o the surface.
This conclusion is strengthened by the observation of lhlozemoff and Kam-
sey (1317who found that the operating rapacity of a mechanical flotation cell is
chiefly dependent upon that volume of the cell through which air bubbles are
passing. Design of the cell i d 1 influence the aerated volume but cannot mark-
edly influence the supersaturation of dissolved air produced hg the impeller.
In a pneumatic cell supersaturation is still possihle but is smaller than in the
T h e term “rate of flotation” is used in this paragraph in the sense of the number of
particles floating per unit time rather t h a n in the sense of the weight of mineral floating
per unit time.
396 I<. L. SUTHERLASD

mechanical cell, and the opei ation iiiiglit have been expected t o provide evidence
€or the encounter hypothesis. Unfortunately, in the usual operation or” a pneu-
matic cell the large amount of air used obscures the process, since it s ~ ~ e e much
ps
pulp into the froth. The life of bubbles in the froth is five to twenty times that
in the pulp, so that the mineral adheres nhile in the froth. Plante and Suther-
land (16) hare dewribed a process for separating ergot from rye by pneumatic
flotation : the floating particles (grain) were never carried mechanically into the
froth. The coursing air bubbles collided and adhered to grain, the most effective
part of the cell being immediately above the bIanket through n-hich air was in-
troduced. Gaudin (Gb) also considers that the probability of encounter in the
agitation cell is higher than in the pneumatic cell because the bubbles are small
and hence provide a large collision area per unit volume; they have a longer life
in the cell and the ratio of mineral size t o bubble size is greater than for the pneu-
matic cell. These intuiti~-eideas are not entirely correct, but with modification
the argument is sound.
Precipitation of gas on hydrophobic surface may be n great help in flotation.
Most flotation operators are familiar with the more rapid flotation of a mineral
or coilcentrate n-hich i 5 heing refloated. Hallimond (10) showed that preagita-
tiori of xanthate-treated galena nith air greatly increased the rate of flotation.
Usually the induction period (-ee page 401) is greatly decreased on a mineral
surface if previous contact has been made n-ith an air bubble. This behavior
has been ascribed t o thin layers of nir on the mineral mrface, e.$., the observa-
tions of de Witt (27) on covellite, and of Harvey e2 al. (11) and of Pease and
Blinks (1 5 ) on hubhle niiclei, which are important in determining the behavior of
liquids.
If gas precipitate> on rnirieral particles during flotation in a cell, subsequent
flotation niay still be ascribed t o collision b e t m e n an air bubble and an aggre-
gate corisisting of a iiiineral particle and a minute air bubble. The aggregate
may have a density greater than 01’ even less than that of the pulp. The theo-
retical approach adopted in this paper nil1 still be valid, but for the smaller sizes
of mineral the aggregate will be very much larger than the particle. It then
follows from our theory that the chances of an aggregate floating are better
than those for the mineral particle 1,y itself, particularly in the smaller size
ranges.
111, ISSI‘MPTIOSS IS THEORETICAL TRCATJIEST O F FLOTATIOK RATE, USING
THE DIRECT ENCOUNTER HYPOTHESIS

111 1832 Gaudin (Cjc) (*onsideredcolliqion between an air bubble and a mineral
particle in a flotation cell, awiming that ( A rmter is non-viscous and incom-
pressible; ( 2 ) \\ ater i- infinitely divisible (i.e., the mineid particles are large
compared n itli tlir moleculcs or their meail free path) ; ( 3 ) bubble and particle
( 6) tii~hblea i d p:irticle :ire the only disturbing factors in the
cell; (.j)niotion 01 1)uhble and particle is irrotational (i.e.*there is streamline
motion uf t l p 11 titer pa\f these s p l i c i d . IIr deduced that collision is possible
only if thc cwi1cy of the particle lies on the rentral line of motion of the bubble.
 KISETICS O F THE FLOrATIOK PROCESS 397

His malysis, hoirever, T X I ~b a w l on an implicit, hut eiwnwus, a-wmption that

two bodies move independently i n a fluid, thnf i4, there i q no intei.nrtion of thc4r
velocity field,.
The motion of tn-o spheiw t on-aid one another hi not hrcw succe-sfully
analyzed except when the spheres move aloiig their line of (’enters ( 1 7). llathe-
matical treatment i b po4hle. honever, if the ma- of one of the bpheres is zero,
Le., if the particle is inertia-le-; it uill then travel along a stieamline of the liquid
passing around the qecond *phere. Oiir treatment of collision in an ideal fluid
rill t>mhodythe awimption that inritial effect< he neglected for the .ni:iller
sphere. The question of the forceq of adhesion b e t w e n the air bubble and min-
eral being sufficient to pievent the aggregate parting is diicutsctl in Section TX,
Considering these assumptions in detail. n e may say n i t h reqpect to the first,
that the results obtained for a non-viscous, incompressible fluid are an excellent
approximation to the behavior in a viscoiis, dightly coniprewible fluid s i i p h as
n-ater.
The second assumption nill lead to significant errois only if the size of the
particle (or air bubble) is le*>than 0.1 micron. Particles as wiall as this nill not
be considered.
Particles are not spherical, h i t n e can define a hpherical particle which he-
haves essentially as the mineral. Calculations based on this assumption for
other hydrodynamic problems show a good approximation to actual behavior.
Departure from sphericity of the bubble is more serious. The bubbles are de-
formed (flattened on top) and the motion of bigger bubbles shon-s instability
(oscillation). Hence the velocity of the bubble relatire to the particle used in
this paper vi11 be determined from an esperiniental cquation clesciibing the
motion. There will be an error, honever. in deriving the “colli4on area”. 71-hich
error is difficiilt to evaliiate.
The moyt serious error t i p p ~ a r ti o be in :wimption -1. It i- implicitly assumed
that ( a ) there is no coalewence of bubbles: ( 1 ) ) huhhlei do riot cluster around one
particle (19): (c) buhbles do not hinder each other while ri4ng (i). AIF;siimption
( a ) was proved valid by experiments debcrihed in Section IX. lye have riot
studied the importance of factor and farlor (c) i i *hoTI-n in &IppendixI to be
relatirely unimportant.
;1seuniption 5 is not seriously in error, though for the bubhle ,-ize,; studied the
motion is not completely streaniline (irrotational). The theory can be applied
into the region of tmbulent fiov-, e g., Stokes’:, lair (’an he extrapolated n-ell into
the region of ttiihiilence n-ithoiit errors eKceeding. say, 10 per cent.
Seglect of inertial effect? (asslimption 6) slightly lowers the calrulaterl col-
lision rate for the small partirleq common in flotation.
IV. SYMBOLS USED IU THE THEORCTICAL TREATMEST

-1 = o\-erAon- rntc of froth from re11 per iinit of re11 rolurn? ( v c . - ’

f?= h l l ( J ~ a n c yforce on the hitbble
P = constant of integration. irhich is rletrrmind h?. the -ti(vtrnline
(,tinsen
398 E;. L. SUTHERLASD

L) = maximum distance at which the center of a particle can lie from

the line of motion of the bubble (figure 1) for collision t o be
possible (cm )
d = d e n d y of mineral particle to be floated ( g . ~ m . - ~ )
d,,, = density of pulp ( g . cm.-')
E = distance of particle from center of line of motion of the bubble
(cm.)
8' = Stokesian resistance to a sphere
/ /
f = U ' f U'O
G = grade of unfloated pulp
G, = grade of concentrate
g= acceleration due to gravity (980 cm. sec.?)
h= height of attached bubble
k , kl, Ji?
= constant.
1
= distance travelled by bubble in cell (em.)
L = capillary attraction of particle and bubble corrected for hydro-
static forces
-1-= number of particles removed per unit vohime of pulp after time
t see. (crn.-')
SO= number oi particles initially present per unit volume of pulp
(c n1.-
-I*'= number of bubbles per unit volume of pulp (em.- ')
AS, = num1,er of particles of radius r per unit volume of pulp ( ~ m . - ~ )
A S A = number of particles \lit11 an induction period A initially present
per unit volume ( c m . 3
&So = number of particles of radius T initially present per unit volume
(em-?
AA17k= number of bubbles of radius R per unit volume of pulp (~rn.-~)
n = number of collisions per unit time (set.-')
nf = number of fruitful collisions per unit time (set.-')
rnf = number of fiuitful collisions in the cell between bubbles and
particles of radius r crn.
lnf = number of iruitiul collisions when bubble is loaded
n L = number of particles attached to a bubble
P = volume of pulp entering cell per unit time per unit cell volume
(set.-?
Q = weight of mineral particle in n-ater
p = 37ro sech? ( --
~ ~ ) R r ~(sec.1)
~ \
 KIXETICS OF THE FLOTATIOS PROCESS 399

ArRm = rate of flotation of particles of radius I' ( g . set.-' ~ m . - ~ )

A R R m= rate of flotation of particles by bubbles of radius R (g. set.-'
~m.-~)
s,,,= average rate of flotation (g. set.-' cm.?)
,R, = rate of flotation of sample containing only particles of mean
radius
f R , = rate of flotation from cell in continuous operation (g. see.-'
ernsp3)
,Rf,, = rate of flotation horn cell in continuous operation when condi-
tions are steady (g. see.-1 ern.?)
tR, = rate of removal of ore in tailing (g. sec.-1 cm.?)
T , TI, 7-2, rk, r, = radius of particles (cm.)
s = distance travelled by particle on bubble surface (cm.)
t , = time of contact betn-een bubble and particle (sec.)
t = time variable (sec.)
T = surface tension (dynes cm.-')
V = velocity of bubble relative to the particles (em. set.-')
P = velocity of average-sized bubble (cm. set.-')
1'' = velocity of particle around bubble surface, arcial velocity (cm.
see.-'>
TT- = total weight of gangue in concentrate (g.)
ec = concentration of mineral removed from pulp after a time t
sec. (g.
zco = Concentration of mineral in the feed (g. ~ m . - ~ )
zc: = concentration of gangue in the pulp (g. ~ r n . - ~ )
t c i = concentration of gangue in the overflow liquid (g. ~ m . - ~ )
w C = concentration of mineral removed from unit volume of pulp
into the concentrate a t a time f (g. ~ m . - ~ )
tc; = concentration of gangue removed from unit volume of pulp
into the concentrate a t a time t (g, ~ m . - ~ )
Ar" = concentration of particles of radius T removed from the pulp
after a time t (9. c m . 7
ArwO = concentration of particles of radius I' initially in the pulp (g.
~m.-~)
R: = polar coordinate
a = contact angle measured from mineral through pulp
p = radius of curvature of bubble in the planes perpendicular t o
the plane of contact
PO = radius of curvature of bubble a t its apes
6' = proportion of particles retained in the froth after fruitful col-
lision
4 = velocity potential of the liquid relative t o the bubble
X = induction period necessary for air-mineral adhesion (sec.)
9 = viscosity of pulp (poises)
v = kinematic viscosity of the pulp (stokes)
 400 K . L. SUTHERLBSD

u ='density of air bubble (g. cn?)

a,:=jdensity of gas in air bubble (g. mi.?)
4 = polar coordinate
# = probability of gangue adhesion
{(T, R, etc.):= function of T , R , etc.
V. COLLISION BETWEEN BUBBLE AND PARTICLE

Ramsey (17) shows that the equation to the streamlines of a fluid moving past
a sphere of radius R (the bubble) is
C'X
sin2 4 = ___
x3 - R3
where (z, 4) is the polar coordinate of the streamline (figure 1). As the inertia-
less particle will travel along a streamline it will just touch the bubble if it is
travelling on the streamline whose closest approach to the bubble is r cm., the

FIG.1. P a t h of particle in streamline

radius of the particle (figurc 1). This streamline v-hich passes through the point
z =E + T, 4 = ciiitbl~si i b to determine the constant in equation 1, ciz.:

C' = (R + T ) -~ R3

R f r
\lThen the particle is at an infinite diitance above the bubble, then 4 = 0 and we
require the value of s sin 4 vhich is equal to L ) em., the maximum distance a t
which the center of the particle ran lie from the center of the line of motion of
the bubble in order to j u i l collide nith it. Subgtituting in equation 1, we have

and taking tlie limit as + + 0 ii.c., R' ----f .t)

If, as is true in flotation, i' is smnll comparcd u-ith R,t h m terms containing r3
only will he negligible and hence
I1 = 4 3 2 (4)
r ,
Ihis cIu:intity, I ) , defines t h e "collision radius" of thc htbhlr for i? particle of
radius r . Llllparticles lying n-ithin Ihis dietnncc from thc line of motion of the
 KISETICS O F THE FLOTATION PROCESS 40 1

bubble will collide with it. The number of collisions per second (71) between
the bubble and a suspension of particles ( S o per ~ m . is
~ therefore
)
n = = 37~RrV~l~~
TD~V.I-~ (5 )
where V is the velocity of the bubble relative to the particles. If the bubble is
an oblate spheroid (about the axis of motion) the number of collisions is
n = 3X-nRrVLYo

where tk is a factor which is less than unity, the amount depending upon the eccen-
tricity of the ellipsoid ( R is here the radius of the ellipsoid perpendicular to the
axis of motion).
If S’bubbles are present per cubic centimeter, the number of collisions is
n = 3aRrVX0S’ (6)
VI. RATE OF FLOTATIOX

The rate of flotation is assumed to be governed by the rate of collision be-

tween mineral and air bubbles in the pulp. It is observed that bubbles some-
times drop their load when they reach the froth, ou-ing to coalescence and sub-
sequent decrease in area of surface holding the mineral. T5’e will suppose that a
fraction (1 - e) of the particles is returned at any instant to the pulp by coales-
cence either a t froth-pulp interface or in pulp owing to coalescence of bubbles or
to some turbulent condition which will strip the particle from the bubble. Usu-
ally e will be close to unity.
If the bubble is practically completely covered with particles before it has risen
into the froth, the last part of its journey t o the surface is ineffective, for col-
lision cannot lead to adhesion. If the pulp density of floating mineral is large
or the grade of feed is high (as it is in cleaning operations) then “crowding” be-
comes important. Under usual conditions the “collision area” on top of the
bubble will be free from particles which slide to the bottom of the bubble (3).
I n addition to the above factors, not every collision will be fruitful, since a
finite time of contact between bubble and particle is needed t o ensure adhesion
(the induction period A ) . This period is of the order of magnitude of 0.005-0.1
see. ( 5 , 20), although in special systems it is considerably longer (25). TYhen a
particle is a t a distance d z r cm. from the line of’ motion of the bubble, it is
obvious that the bubble will only be touched for an infinitesimally short time
before the particle leave> it following the streamline flow of the liquid. As the
particle lies nearer to the line of motion of the center of the bubble, it nil1 be in
contact for longer and longer periods before it reaches a position where it can
leaye the bubble. Let the particle be E cm. distant from the center of line of
motion of the bubble. Then the point (s = +I?,+) at nhich the particle
strikes the bubble surface is derived from equation 1.
Since lim (asin Q ) is equal t o E , the constant C‘ is ecliial to E’. Equation 1
z-m

becomes
402 K. L. SUTHERLASD

and the polar coordinate of the point n-here the particle strikes the bubble is

x = r + R, 4 = arsin E

or neglecting r3
+ = arsin (E/.\/=T)
The velocity potential of the liquid relative t o the bubble is given by

The arcial velocity-

Although the center of the particle travels on a circle of radius (12 r) after+
touching the bubble, we may consider it as moving on a circle of radius R with-
out being in error by more than 10 per cent for the size of bubble and particle
usual in flotation. This simplification is used in equation 15 and subsequently.
From equation 10

+
The time to travel from the point (12 I’, (6) where the particle collides to the
point ( R +
r , s - 4 ) n-here it leaves the bubble is given by

dS
since dt, = - and ds = ( R + I’) d+ is the distance travelled on the bubble surface
V’
in a time dt,.
Hence

Substituting for 4 from equation 8

2 A more accurate approximation would be

 KIKETICS O F THE FLOTATION PROCESS 403

If the particle is to adhere t o the bubble, then the induction period A must be
less than or equal to t,.
Equation 15 then defines E for a given A :

Figure 2 shows equation 14 plotted for different values of R arid X and also
s h o m the effective area of contact for each bubble after reducing to unit volume
of air. T' is calculated from ,Allen's equation (see -Appendix I).

Radius( R cm)
FIG.2. The relationship betn-een ( a ) bubble size arid the effective contact radius E and
( b ) bubble size and the effective area of contact per unit volume of bubble (EZ/R3).

We non- replace equation 6 by

where ?I,+ is the number of collisions per unit time per unit volume which lead to
adhesion.
The rate of flotation (g. ~ m . set.-')
-~ is then

n-here 0 is introduced to allow for particles removed from the bubble after fruit-
ful collision (page 401) and d is the density of the particles. Hence I?,, is pro-
40-1 K. L. SUTIIEKLAND

portional to the pulp density and the rate of‘aeiation. It is directly proportional
to the radius of the mineral h i t is related in a more romples niariner t o the
bubble size, z i x : RT- qech’ (y;)
__

Suppose that in a batch cell the rate of flotation i:, qtudied uitli time. I,et
w o g. ~ m . -be~ the initial concentration of the niineral. Then if ( v ~
- u‘) is
the concentration at f s e ~ .the
, ~ rate of flotation is giren by

where p is a constant. Integrating h e t n w n the limits 0 and t

t = ~ ~- (e P1)
u i 20)
-3
But a t the concentration (zco - w) g. cam. we haye from equation 18

where S o and S itre the number of particles per ~ m of. cell

~ pulp which were
present originally and which were removed re;spectively, i.e., (So- -Y)is the
number remaining. Since

me have from equations 21 and 22

R,, = 390 seclil (g) RrVS’(wo - UJ) (23)

Comparison of equations 19 and 23 s h o w that

p = 390 sech’ (,,>3 1’X IZrVS’

and hence equation 20 becomes

-3rOsech?(?rX 4R)RrF.Y’t 1
w = wojl - e I (23)
and substituting from equation 23 in equation 23 for 10, U P c a n tierire the varia-
tion of rate with time.
il Denver subaeration flotation re11 of depth 25 em. roritains 104r n of~ pulp.~
The follon ing values are typical:
R = 0.03 cm. I’ = 3 x 1W’cm. I’ = 6 cm. ace.
- I

S’= 20 brtbbles em.-’ 8=1 ti’il = 0.01 g. mi. *’

3 S o minerd will appear i n the froth uiitil :t time t sec. a f t e r aeration co~iiinencea,i.e.,
until bubbles have risen from bottom of cell t o the top. t is dependent upon bubble size,
Vt being equal t o the depth of the (%ell. The tinw can br considered as starting after this
initial period.
 KISETICS OF THE FLOTlTIOX PROCESS 405

-1typical time reyuired for a 90 per cent recovery is GO sec. (e.g.,for sized quartz
floated with cetyltrimethylammonium bromide). 'Then from equation 20 the
d u e of X is 0.009 sec., a value which is plausible.
It is generally knoivn that the rate of flotation iq governed approximately by
an exponential lan-. Thub Beloglazov ( 2 ) ,Zuniga (28), and Grunder and Iiadur
(9) found that the rate of flotation at any time \\-as approximately proportional
to t h e amount of floatable material remaining in the cell.
VII. VARIBTIOS IX GRADE OF COSCESTRATE KITH THE TIME
WHET\' GASGI-E IS PRESEXT
Let zcg g. cm.-d be the initial concentration of mineral to be floated, and ~ ~ g.' 0
cm.-3 the concentration of gangue. Let $ be the probability of flotation of
+
gangue after collision ($ to include the sech and 0 terms). Since will be small
and u ( is usually large compared with tr0 we can, with good approximation,
consider L U ~ constant throughout a batch test.
Mineral and gangue n-ill be carried into the concentrate by the walls of the
bubble cells. The extent of draining (proportional to the height of froth) deter-
mines the amount of pulp left in the walls. This pulp will not have the same
composition as that in the cell, because gangue and mineral settle from it. I n
the mineral concentrate, the overflow of liquid is d sec.-l per ~ m of. cell
~
volume carrying Aw; g. sec.-1 of gangue into the concentrate (IC; = concentra-
tion of gangue in the overflow liquid). The value of w;may be considered con-
stant throughout the experiment and, judging from Schuhmann's results (18),
may have values between 0.5 Z P ~and 0.1 for sizes of particles of less than 7
microns and 35 microns, respectively. The coarser the mineral the more
rapidly does the gangue leave a froth.
The grade of the feed is

If we,wi are the weights of mineral and gangue, respectively, in the concen-
trate (produced from 1 cme3of pulp), then the grade is
ZL', . l-G,-wb
G, = ___ i.e., -- - (27)
'lcc + VI- cc a',
From equation 23 for the gangue
R,t = 3n-y5RrVLV'w!$!
= p'$u(t
where p' = 37rRrX'T'.
I n the same time .iwSt g. is carried over by the froth liquid.
The total weight (11') of gangue appearing in the concentrate is
TI' = p'$zcit + AW;t
= u 4 { p'$ + ,L41 (29)
406 K. L. SCTHERLAXD

I /
where f = i t f ,t~~ is constant for any >ize range and has values less than unity
and greater than zero.
The amount of mineral floated in the time 1 is and from equations 25, 26,
u i .

27, 28, and 29 rve have:

If, in a batch float, the grade of concentrate is studied, then it is apparent

from equation 30 that the grade falls steadily as time increases.
VIII. RATE OF FLOTATIOK O F I I I S E R A L WHICH EXHIBITS A SIZE RANGE
Hitherto the mineral floated has been considered to be of uniform size. Since
the rate of flotation depends upon r. the radius of particle floated, the average
rate of flotation does not equal the rate of flotation of the average size particles.
I n the analysis which follon-s the presence of gangue is neglected.
Let the number of particles A S , with a radius between r and r + Ir be given
by
AL\-, = -\-"{(r)Ar (31)
where { ( r ) is a bize-distribution function.
Corresponding to equation 17 n e have that the number of' fruitful collisions
+
for particles in the size range r , I' Ar

and the weight of mineral floated in time Af is

If AriYo particles of radius between r and I' + Ar are originally present and
AX, are removed after a time f, the rate of' flotation i.;

and

Hence
 I i I S E T I C d OF THE FLOTATIOS PROCESS -1-0’7

and substituting for &ZL< in equation 33 from equation 3 5 :

I,R?,,= 3 d sech’
(Y3
--
RT--\-I Tl,,wo e--3a9srch2 [ 3 i ‘ h / 4 R )R r V.\-‘t

The total flotation rate is the sum of the flotation rates for each size of pai6cnle,
am1
4
&ZL?, = -- 7ri”Yo Cl<(T).h
3

The effect of a partic4le t1isti~il)utionand correlation with espei~iment:di ~ c i i l t s

is disciissrtl in -1ppentlis 11.
IS. R l T E OF FLOT.ITIOS B T UL-BHLES JTHICH HAVE A SIZE D I S T R I B U T I O S

\\-ith a rat1iu.s betmen X and I?

1,rt the numher of 1)iil)I)le.~ + AI? he gil-cn 1137
= .\-’[(I?)AR
I-\-; (36)
\\-e nxiy c1cril.e the rate of flotation :dong line iniilar to that emplo>-ctlfor the
particle-size clistrilmtion. The i.es;ult has a foinial i,esemhlanc*rt o cciiiution 36.
Ho\\-ewr, the 1~uhl)le-sizetlistidiution. iinlike the pnrticlr-size tlistrihution, is
independent of time. (‘onsidering therefore flot:ition diic t o 1 ) i i l ~ I ) l ~ofs size
lwt\\-ccn R antl X +
111‘vm., equation 23 1)econit.s

&RnL = 3nO sech- ” (g) - w)IR

RrT7[(I?)A\7‘(~~t (3i)
antl therefore

la clRRn, = I?,it= 3 7 r 8 ~ ( -
~ ~IC),.\-’ Lrn T7Rsech? (=)
31-x
[ ( R )clR !38)

l.C..

since

l a { ( R ) dR = 1 f40)

a r i d the mean radius of the hiihble is defined from

The value of T’ ah a function of R is given by equation 62. Equation 39 can he

integrated as previoiidy.
 KIKETICS OF THE FLOTATIOK PROCESS 4ci9

To obtain the distribution in bubble size a 2000-g. Denver subaeration machine

with a glass side was photographed. Figures 3a, 3b, 3c show the effect of 2.5,
5 , and 10 mg. of pine oil per liter of water, respectively, on bubble size u-hen the
impeller was rotated a t a Ion- speed to avoid excessive froth. These bubbles
were illuminated by a lamp which gave a flash of 10 microsec. ,111 motion of the
bubbles was thus “stopped”. The distribution in bubble sizes is given in figure
4. It will be noted that nearly all bubbles are spherical. By measuring the
depth of focus of the photographs the number of bubbles per cubic centimeter of
pulp could be calculated. Thus there n-ere three, seven, and twenty-five bubbles
per cubic centimeter of pulp in the photographs reproduced here.
Cinematographic records n-ere made a t speeds between 800 and 2000 frames
per second, using an arc lamp for illumination. These again showed little or no
departure of bubbles from sphericity, no coalescence with one another, and

FIG.4. Distribution of bubble sizes corresponding t o aeration and pine oil concentra-
tion shown in figure 3.

uniform speeds of ascent. The speed of the fluid flow n-as measured from sus-
pended spheres of density equal to that of the pulp.
T’olkoT-a (22, 23,24) has calculated the force of adhesion between an air bubble
and mineral particle when the latter is small. If the particle is not free to move,
then the force separating bubble from mineral is the buoyancy of the bubble.
Since the area of adhesion must be small on a small particle, the force of adhesion
is also small. Yolkova confirmed his theoretical calculations experimentally
and then stated that the force parting bubble and mineral 71-hen these collide is
determined by the buoyancy force on the bubble. This is not correct for move-
ment in a fluid. His subsequent argument leads to the result that for all par-
ticles there is a masimum size of bubble which can adhere and that for small
particles these bubbles are so small that flotation does not seem possible: firstly,
because the rate of ascent of these bubbles is far too small and secondly, such
bubbles will normally disappear by dissolution. I n the photographs shown in
figure 3 bubbles smaller than 0.002 cm. radius have been neglected. I n figures
410 IC. L. SUTHERLAKD

3a and 3b there are about ab many bubbles of, say, arerage radius 0.001 cm. as
there are bubbles of radius greater than 0.002 cm. Severtheless they constitute
an insignificant proportion of the air passing through the cell and they have an
average terminal ascending velocity of about 0.02 cm. set.-' which will not allon-
them to escape from the pulp. S o n - the esc'ess pressure over atmospheric
inside a bubble of radius 0.001 cni. is 0.14 atni. Hence these bubbles \\-ill dis-
solve readily and the gas will he precipitated on the mineral (vide reference 21)
and on larger bubbles.
I n a viscous fluid the parting force is not the buoyancy of the bubble but the
viscous drag on the particle and its ovn weight in the fluid. Xs the particle
slides down the bubble it, attains much of the velocity of the bubble surface.
The radial velocity of the particle is determined from the velocity potential ,t
(equation 9) of the fluid
- _- 17 cos 4 - cos
I-R~T-? 4 (42)
ax
This is a maximum for 4 = x. Pince the particle is attached to the bubble, .2:
has the value ( R +r ) and

(z)mnx[(g-J
= - 11 = - I
- 3rR
(42a)

The negative sign indicates that the radial velocity is in the direction away from
the center of the sphere. The viscous force, F , on the particle will not exceed
the Stokesian resistance, Le.,

The only other force attempting to separate bubble and particle is an impulsive
force, I , due to the inertia of bubble and mineral. From the principle of con-
servation of momentum (considering viscous and gravitational forces absent,
as the effect of these are calculated above) the terminal velocity of the aggre-
gate, bubble and particle, may he derived as

(43a)

where li, -L' are the upward velocities of bubble and particle, respectively,
before attempting to separate and the remaining terms give the apparent masses
of the bodies concerned. Equation 42a gives the yelocity of the fluid and hence
of the particle, relative to the bubble. IVhen the bubble moves with a velocity
V ,then the velocity of the particle immediately prior t o the attempt a t separa-
tion is

The difference het\\-een the initial and final yelocities given in equations 431
 KISETICS OF THE FLOTATIOS PROCESS 411

and 43a, respectively, divided by the time, t see., in which the velocity is chang-
ing, enables the impulsive force, I , to be calculated:
$aR3r3d,(d - d,) T' j' 3rR
I =
R3d, +r3(d - d , ) 7 \(R T)? + (43c)

Seglecting the smaller terms, we obtain:

12nr4 T'
I<-
Rt
TABLE 1
Comparison of the adhesional force ( L ) ,the weiqht and Stokesian resistance (Q F ) , and the +
buoyancy of the bubble ( B )
+
Stable adhesion when L > Q F . CY = 45'. Velocity of ascent from appropriate Reynolds
number and coefficient of resistance. Density of irticles = 4 g.cm.-3
DIAMETER OF
PARTICLE
Q f F R

microns cm cm sec-1 d>nes dines 1 dynes

25 I 0.40 8.1 x 10-4
50 0.78 3.9 x 10-3 ~

75 1.1 x 10-2 28.2

100 2.1 x 10-2
200 1.3 X 10-1 1
500 1.7

2.5 0.39 9.9 x 10-4

50 0.75 4.6 X
75 0.18 18 1.08 1 . 2 x 10-2 2.99
100 1.39 2.3 x 10-2
200 2.35 1 . 3 X 10-1
500 3.80 1.7

Table 1 compares the value of F +

Q, where Q is the weight of the particle
in the fluid, with the buoyancy force of bubbles (I? = 4rX3d,g) and the adhe-
sional force L which is given by K a r k (26) as

Id = srT sin a - -
s>
where a is the contact angle, I' the surface tension of the pulp, r the radius of
(44)

circle of contact, and p the principal radius of curvature a t the circle of contact in
the plane perpendicular t o the solid. T o calculate p it is necessary to know the
forces acting on bubble and particlr. Thu.: \\-ark's equation for the bubble
contour becomes

where po ir the curvature of' the hubblc a t its apex and it is the distance of the
412 K. L. SUTHERLAHD

apes from the plane of contact. X-olkova (23) s h o w that for small areas of
adhesion 1%may be put equal to 2 R , the diameter of' the bubble before adhesion,
and that po is approsimately equal to X. Thus:

The (Q + F ) term replaces the usual buoyancy force due to the bubble. The
impulsive force is probably so small that it can be neglected. It can only be
large if t is small (equation d3d). For the example cited in table 1 the impulsive
force does not exceed the adhesional force, L , except if the particle can be de-
tached from the bubble in less than sec. Thib is not feasible and for a
period of even so short a time as lo-? see., the force is from 30 to 10' times smaller
than L , and is aln-ays smaller than the (Q + F ) force.
Calculation from equation 46 s h o w that the bubble shape involves no re-
entrant surface and consequently the aggregate is stable. It is apparent that
the adhesional forces are sufficient for flotation however small the particle.

X. RATE OF FLOTATIOS OF A SAXIPLE THE PARTICLES OF WHICH DO S O T

HAVE A CXIFOIIXI INDUCTION PERIOD
Let the number of particles AAlvh \vliirh have an induction period between
X and X +AX sec. be given by:
L1-A = S,{(X)AX (47)
Then an analysis corresponding t o that in the preceding section leads to

where p' = 3xRrT;S' and zuc = + ~ r ~ ~ Y ~ d .

Corresponding t o equation 25 the weight of mineral floated a t a time t is given
by
' B t sechz (3VX/4R)
I dX

(49)

Since the total number of particles originally present in the sample is A-0,

it follows from equation 4 i that

Hence equation 49 becomes

(51)
 KISETIC,S O F THE FLOTATIOS PROCESS 413

If n-e put z = p'0 swh" __

" (y;) , then equation 48 becomes

TABLE 2
Weight of mineral (w Q . ) Pouted i n a D e n z o cell originally containing w o g.(= 469 g . ) of
spheres a f t e r carious times t sec.
wo - w
-
0
wo

30 182 0.6119
60 333 0.2857
120 385 I 0.1791
180 408 I 0.1301
240 420 I 0.1045
300 427 0.0896

It is shown in -Appendix I11 that the second integral is negligible for certain
numerical values of p'0. If it is neglected, then the inverse Laplace transforma-
tion can be applied and the integral i.j

(33)

where i = 47.
If therefore a batch rest is made in a flotation cell and an analytic function
determined empirically for (vi) - zu), z c o from the experimental data then, pro-
vided this function fulfils the condition. of the I.aplace transformation, the
function {(A) can be evaluated.
To evaluate the distribution likely in a flotation pulp, spheres of a calcium
glass n-ere prepared. The fraction betn-een 52 mid 7 2 mesh was separated and
each particle allon-ed to roll don-n an inclined slope. Only those which n-ere
completely spherical rolled straight and w r e collected. -1sample was photo-
graphed. and more than 98 per cent of the particles n-ere spheres. The average
diameter vas 0.0252 cm. -After cleaning by ignition a t G5OoC.,the spheres were
floated in a 2000-g. subaeration Denver cell, using 20 mg. of laurylamine hydro-
chloride per liter as collector and frother. The pH value as 7.0, the tempera-
ture 20°C. The rate of air flon- into the cell n-as constant at 55 per second.
The weiqhts of concentrate taken at various times are shown in table 2. The
414 E;. 1,. SUTHERLAND

low rate of air flmv \\as essential t o enable e a s - removal of the concentrate:
a t the full rate the float I\-as over curnpletely in less than 1 min.
From table 2 an analytic function relating (w0- I w0 to the time t with an

accuracy of better than 1 per cent and nf the required form is

x
+ r ) 3 +--(47.46 +
-w -
1 ~ 0 1.614 X
- ______ - ____22.62 2.747 10‘ 2.39 X 108 (jq)
~

100 (47.46 + f)’ (47.46 + (47.46+ t)5

Integrating equation 53 after subhtitution from equation 54 we have:

i1.614 X LOw8 - 11.312 + 4.578 x + 9.975 X 106z3} (55)

10’~‘

0 4.Q05 0.om 0.0,s o.oz0

h
FIG.5 . Distribution in values of the induction period for flotation of spheres

For the sample studied it is assumed that 6 is unity and the following measured
values r = 0.0126 em., R = 0.064 cm., T’ = 12 cm. set.-', S’= 5 bubbles ~ m . of-~
pulp enable p’ t o be calculated. The value of z is found from p’ sech’ .)Y;
~
x
plot showing A4Vh’ X Ois given in figure 5. The curve s h o w a typical distribution
of X values.
With a sample containing particles with different induction periods the curve
relating weight of mineral floated with time will no longer be a simple exponential
one. Calculation of the effect of varying induction period on the rate of flota-
tion under continuous operating conditions is difficult, but qualitatively the
result resembles that for a distrihution of particle sizes (see hppendix 11).
XI. STATE OF COSTIAXOCS OPERATIOS

I n correlating the batch test and a continuously operating cell, factors such as
the accumulation of soluble products which may affect adsorption of collector,
 KISETICS OF THE FLOTATIOS PROCESS 415

rate of adsorption of collector, etc. are neglected. Let the rate of flow of ore into
-1
cell be Pw0 g. sec. , where P ~ m per ~ cell volume is the volume of pulp
. C~ M . of
entering the cell per second. At a time t , the total weight of ore that has been
in the unit volume of the cell n-hich originally contained w0g. of ore is
(1 + Pow0 g.
The weight of ore floated per unit volume of cell when w g. has been re-
moved is
f R t n = p(wo(1 +
Pt) - U ' ] (56)
At the same time mineral is removed in the tailing a t the rate
tKn, = (P - A ) jU'o(1 + Pt) - w 1 (57)
where A is the volume of liquid removed per second per unit volume of cell
with the concentrate.
+
The total rate (fRn8 iX,n) is

(58)

For the boundary condition t = 0, ut = 0 ,

(59)

where p is as usual. Substituting for u1 from equation 59 in equation 56 the rate

of flotation is
f R m
-
- (60)
When t is large (steady conditions) equation 60 becomes

k2 r
This equation is of the form -
1 + A3
and will be of value in determining the vari-
ation of rate of flotation with size in continuous test. IRA can be calculated from
batch cell tests, since p is deducible from these.
If we calculate the ratio of equation GO to equation 61 then we obtain curves
of the type shown in figure 6. Data presented by Schuhmann (18) for the rate
of flotation of a copper mineral with time are also plotted in the same figure.
The experimental curve cannot be accurately described by an equation of the
type given. This is discussed in A%ppendixI1 of this paper, where Schuhmann'n
curve is shon-n t o he compounded probably of a number of esponential Curves.
X I . VrlRIATIOS OF FLOTATIOS HrSTE WITH P.IRTICLE SIZE

'l'lie variation in flotation rate for particlei of different size in continuous flow
P - 3
tests is drdiicwJ from eqiiation 61. Figure 7 b h o w c u r v c ~for n-hich ___
P
4l(i K. L. SUTHERLAND

t0 40 60 80 /oo 120 no an /e0 Coo

T/M€ - t SECQVDS
FIG.6 . Ratio of flotation rate t o rate under steady conditions during a continuous test

PARTICLE SIZE - LOGARITHMC SCALE - r ,n MICRONS

FIG.7 . Relationship betffeen rate of flotation and size of particle floated during con-
tinuous tests.

is varied and data obtained by Gaudin, Schuhmann, and Schlechten (8). The
curve does not fit the smaller values of r and unfortunately there are insufficient
data to determine whether the flotation rate increases linearly with radius, as
 KIXETICS OF THE FLOTATION PROCESS 417

claimed by the author, or whether it is described by the relation above. Gaudin

Schuhmann, and Schlechten hare suggested that the smaller particles aggregate
to non-aerated flocs. If this is true it is difficult to see why they were able t o
find smaller particles in their method of measurement of particle size. Their
method v a s to follow the rate of sedimentation, n-hich rate depends upon the
size of particle or aggregate. If special precautions were taken to disperse these
aggregates, then their hypothesis may be proved by conducting the sedimenta-
tion experiments without dispersing agents. Because the flotation rate is con-
stant, the number of particles to maintain the size of the flocs constant must
increase enormously as the mineral size is decreased.

D/A*I€T€R OF DROPLETS ( Y / C R O M )

FIG.8. Curve showing‘distribution of particle size in a n emulsion (after Clayton (3))

bliming” is an esample of the flocrulation of small particles on larger ones,

( 1 1

but excellent flotation of mineral is still obtainable nhen the conditions in the
pulp are such that “sliming,” a n d therefore presumably flocculation of small
particles, is absent. I t is poqsible that conditions for *bsliming”were present in
the above experiments.
.An :malogoiis system is shonn in the distribution of droplet sizes in a n emul-
sion. One would expect, a priori, a distribution range from large particles to
almost infinitely sniall particles. Figure 8 4io~rhan actual frequency curre (4).
Dropleti of less than 2 microns are almost completely absent-this being common
to many emidiionq iescliiding those in nhich the viscosity is yery high) and it is
usually postulated that becau-e Bran-ninn morement iq PO marked for particles
of less than 2 micron diameter frequent collisions ensure coalescence, which gives
a smaller surface and hence a decrease in free energy for the system. Khilst
flocculation presumably leads to only a small decrease in free energy due to
118 K. L. SUTHERLASD

diminution in “free surface,” the study of colloids s h o w that flocculation is fre-

quent and is a stable condition. That the rate of flotation becomes constant
when the mineral particles possess a diameter less than 2 microns and that
emulsion droplets aggregate to form drops of the same size may be a coincidence,
but it provides a useful starting point for discussion. O d h (14) has measured
the size of flocs produced by the coagulation of barium sulfate suspensions and
found sizes between 1 and 13 microns, according to the concentration of flocculat-
ing agent. These flocs contained betn-een 50 and 120,000 particles. The flocs
were formed under quiescent conditions, and the larger-sized particles may dis-
integrate if placed, for example, in a flotation cell. S o data are available to show
the variation in size of floc when a standard amount of coagulating agent is added
to suspensions containing particles of different sizes.
APPENDIX I

The effect of bobble loads o n rate of Jlotntiori

Allen’s equation (1) describes the relationship between bubble size and tcr-
minal velocity for the size of bubble common in flotation:

d, is the density of the pulp, u that of the bubble, and v the kinematic viscosity.
For the experimental values used in thi, paper
T- = 229(12 - 0.0034) (63)
Allen only claims that hi3 equation is accurate to a bubble radius of 0.05 cm.7
but his data do not extend beyond this d u e . -in assumption made in our use
of Allen’s equation is that when many bubbles are present the hindered rate of
rise will not differ greatly from that of the single bubble. Gaudin ( 7 ) discusses
the data of Iiermack, N’Iiendrick, and Ponder (12) for solids and finds cor-
rections to the Stokes equation of the order of 5 per cent for an 0.005 ratio of vol-
ume of dispersed solid to volume of liquid. If the same data are typical of a dis-
persion of gas bubbles in water, the error due to the use of Allen’s equation will
be less than 5 per cent, since Allen’q equation is more accurate than Stokes’s
equation.
Efect of load on bubblr : If the bubble carries a load vhich is sufficiently large,
the terminal velocity is considerably derreased. Rewrite -Illen’s equation
I‘ = k,(d,, - ~)~”(h’
- 0.0034) (64)
where

1.1 2 = 0.5y2
--
113 2 / 3
v d,,
The density of the bubble, \\-hen ? l L particles of radiu. I‘ and density d ale at-
tached, is
 KINETICS OF THE FLOTATION PROCESS 419

4
- .lrR3ug
3
+ 43 a r 3 n L d
-

rR3

where u,, = density of the gas. Hence

21 3
T3
d, - ug - - n L d ) ( R - 0.0034)
R3

(66)
since
uo = 0.001 g. cmGP3
Kow the number of fruitful collisions in a distance A1 is

A 1 n j = 3.lrRrNN‘k

If it is assumed that the bubbles carry the full load the whole distance, then we
get an upper limit t o the extent to which loading would increase the flotation
rate.
Taking the ratio of collision rate for loaded to unloaded bubbles we have from
equations 67 and 17:

For d = 3 g. ~ m . - ~r , = 0.005 cm., R = 0.1 cm., d, = 1.2 g. ~ m . - ~and ,

X = 0.0166 it is calculated that 10, 100, and 1000 particles increase the flotation
rate by 0.0, 2.0, and 15 per cent, respectively. The effect is relatively unimpor-
tant unless the particles arr large and the bubble small.
APPENDIX I1

Flotation rate when sample has a distribiition o j particle sizes

Equation 35 gives the flotation rate when the distribution of mineral sizes is
described by a function ( ( r ) . I t is more usual to determine the size range of a
sample by screening and weighing the mineral lying between two screen sizes.
The screen openings are generally related by a geometric factor, e.g., each screen
opening is 1/2 to l/d2 the preceding sizes. We have chosen therefore the
geometric mean of each screen size as representing the sample.
420 K. L. SUTHERLAND

It is convenient to replace the integral of equation 35 by the sum,

where r1, r2 . . . T , ~are the geometric mean si7e of each screening and z~'~{(Ill.)is
the amount of mineral of radius ~ k .

TABLE 3
.lliIl f e e d ( a j l e r Gaudin)
WEIGHT PER CENT ~ SIZE RASGE (DIALIETER IN IAICRONS) GEOMETRIC XEAN RADIUS (MICRONS)

0.5 416-295 175.2

3 295-20s 123.9
7 205-147 87.4
13 147-1 04 61.8
17.5 104-74 43.6
14 74-52 31.0
10 52-37 21.93
7 37-26 15.51
9 26-13 0.10
6 134.5 4.60
11 6.5-0.5 0,902
2 0.5-0 .0

TABLE 4
Rate ofjlotation of each size and total rate compared with average rate
Time (seconds). ............ ... . . ; 10 ~ 50 ' 100 ' 150 ~ 200 ~ 300 ~ 560

I
,R, x 104 I
1 176.1 47.3 16.5 S.10 5.49 2.43 I 1.11

Gaudin has given an average mill feed which will serve as an example ( 6 ,
p. 142) (see table 3). The mean radiu\ for the >ample excluding the 0.5-0.0 micron
size is 35.9 microns. Lissuniing a value of 37d sech? f$)RVA-' of 7.%, the
rate of flotation of particles of tile nican r3diiLs ia

,n R,,,
= 0.02;(ju)oe-o 0 2 S 2 t (74
If the rate of flotation for each of the hize distiibutiona is calculated, then on
summing the%erates we may compare them n-it11 the rate for the average par-
ticle (table 4). For thi, sample the rate of flotation of the sample u-ould be
smaller a t first than that of a sample conristing of the average-sized parricles.
A sample could a130 be chosen such that the initial rate i:, greater than that con-
sisting of arerage-sized particles.
 KINETICS OF THE FLOTATIOX PROCESS 421

The behavior of an ore containing a size range of particles is important when

steady flotation conditions are observed in continuous tests. It will be noticed
above that the variation of the flotation rate with time is no longer a simple ex-
ponential curve but is the sum of a number of exponential terms. If data de-
termined by Schuhmann (18) are examined, the curve showing flotation rate
n-ith time is found not to be a simple esponential curve. This may be due to
either variation in particle size or induction period or both. The ratio of rates of
flotation of initial to steady conditions is given by equations 60 and 61, xhich
have the following form for a distribution of mineral sizes:

where the symbols are as previously and

pl = 3 d sech2 (=)
31'1
RTW

Consider a sample containing 50 per cent of particles of 1l)O-micron radius and

50 per cent 20-micron radius. Here
S!-(lT71) = t(JT2) = 0.5
= 100 x IO-* em., rZ = 20 x io-* cm.
and let PI = 5, A = 5 X and P = 5 X Then

For this sample the arithmetic mean is GO microns, the geometric mean 95 mi-
crons. Hence the rates of flotation of samples of these sizes are

= 1+ 5.ge-0.0345'
(72)
and

Figure 9 shows the ratio of rate of flotation a t different times to the final rate cal-
culated from equations 71, 72, and 73.
The behavior of the sample possessing particles whose size is the geometric
mean of the sample above shon-s an initial rate lower than that given by the
simple exponential function. It is then higher and finally is lower again. This
is the behavior when a single exponential curve is compared with Schuhmann's
data.
422 E;. L. STTHERLAXD

APPEXDIX I11

C'orzditiorzs ;Tor riqlccf o j spcond integral of eyuatio?r 41

From equation 55 we can substitute in equation 52 and deduce the value of
(wo - w)/wo,i.e.

where A = 1.614 X B = -11.31, C' = 4.578 X to3, D = 9.475 X IO6,

p'0 = x , and 1' = 1 + 47.46.

7/U€ -P rp.KC0ND.f

FIG.9. Comparison of ratio of initial rates of flotation t o rate under steady conditions
during a continuous test for a sample with a size distribution of particles and a sample with
particles with the geometric and arithmetic mean.

where
 KISETICS OF THE FLOTATIOS PROCESS 423

ZCC - uq
Thi.; iq smaller than the experimental value of -by the term {l(t) (see equa-
U70
tion 5 2 ) . Son-rl(t) will have its largest value when t 5 0, Le., when 2 = 47.43.
For an accuracy of 1 per cent in the function
U‘O
~
- w it is only necessary that the
WO
ratios of each of the following terms

-4 il
-
23
and -
23
- -
22
+
e-zm ( x 2 m 2 22m + 2), etc.
shall not exceed 1.01. The dominant term for experiments conducted over
periods of less than 1.5 min. is D/z’ and we can consider that the total error will
not exceed twice that in the Djs‘ term. Hence require

$/[$ (1 - e-zm(s4m4 + 4 2 3 m ~+ 122’nz’ + 24sm + 211 1 5 1 . 0 0 ~ (77)

For 2 =

Since x = 3aerRVLYfsech‘
-1
rg)
50 this requires a value of x greater than 0.25.
and assuming that X =

cm., 1’ = 20 cm. sec. , -I-’= 5 then we estimate that the smallest particle size
0.002 sec., R = 0.1

to which this section of the mathematical treatment will apply is 30 microns

provided the constant 47.46 is not altered as particle size is diminished. If
is larger than 0.002 sec. and particularly if the rate of aeration is increased,
this minimum bize can be reduced. It is essential to calculate the error for each
set of psperimental conditions.
SUMMARY

The direct-encounter hypothesis for adhesion of mineral to bubble in a flota-

tion cell is investigated. I t is shown theoretically that:
(I) the “collision area” of a bubble is proportional to the product of bubble
radius ( 8 )and mineral particle radius ( r );
(2) the area over which fniitful collision is possible is given by
)
(z
3rR sech’ 3 T’X

(The induction period (A) almost entirely governs the sech term, because the
ratio of liubble wlocity (17 to its radius (I?) does not alter appreciably.)
induction period? can be calculated and these are probably as accurate
as the experimental value,.;
when there i. a distribution of particle sizes the rate of flotation i b the
sum of a number of exponential functions of time;
when there i. a distribution of hubble sizes the mean rate of flotation
i- equal to tlie late of flotation nith suitably defined mean size of bubble;
w.perimenta1 method6 of determining bubble size and number are de-
hcribed;
424 I<. L. SCTHERLSSD

(6) the variation of flotation rate n-ith mineral size, under continuously
operating conditions, is given hy an equation of the form
r
rate a
T + x.3

This equation fails to predict the uniform flotation rate n-hich has been found by
some authors at small sizes. The possibility of floccillation of particles is dis-
cussed.

The author wishes to thank N r . G. I<.Uatchelor and particularly Mr. ,I.

Pillow of the Aerodynamics Section, Division of Aeronautics, for many helpful
discussions on the presentation of this paper. Dr. I. TT. K a r k very kindly
criticized the manuscript.
The work described in this paper was carried out as part of the program of the
Division of Industrial Chemistry of the Council for Scientific and Industrial
Research, -Australia.

REFERESCES
(1) ALLES, H. S.: Phil. hIag. [8] 50, 323 (1900).
(2) BELOGLAZOV, K. F.: Tsvetnye Metal. 1939, S o . 9, i o ; Chem. d b s t r a c t s 35, 176 (1941).
(3) BOGDANOV, 0. S., A N D FILANOVSKI, ill. SH.:J. Phys. Chem. (U.S.S.R.) 14,224-7 (1940).
(4) CLAYTOX, W.:Emulsions and their Technical Treatment, 4th edition. J. and A.
Churchill, Ltd., London (1943).
(5) EIGELES,hl. A.: Compt. rend. acad. sci. E.R.S.S. 24, 340 (1039).
(6) GAUDIS,8 . RI.: Flotation, McGraw-Hill Book Co., Inc., S e w York (1932): (a) pp.
88-98, (b) p. 96, (e) p. 88.
( 7 ) GAUDIN, A. hl.: Principles of Mineral Dressing, p. 190. McGraw-Hill Book Co., Inc.,
New York (1939).
(8) GAUDIS,-4.hf., SCHUHMASS, w.
R., JR.,ASD ScHLEcIiTEs, A. :J. Phys. Chem. 46,902-
10 (1942).
(9) GRUNDER, W.,ASD KADUR,E.: Metall. u. Erz. 37, 367 (1940).
(10) HALLIMOKD, A. F.: Mining hlag. 74 (April, 1945).
(11) HARVEY, E. S . ,et a l . : J. Cellular Comp. Physiol. 24, 1, 23 (1944); J. Am. Chem. SOC.
67, 156 (1948).
(12) KEmfAcK, w. o.,hf’IiENDRIcK, Ai G., A N D PONDER, E.: Proc. Roy. soc. Edinburgh 49,
170-97 (1929).
(13) hfALOZEMOFF, P., A S D R a h f S E Y , R . H.: Eng. hfining J. 142, 45 (19-11).
(14) O D ~ NS.: , Kolloid-Z. 26, 100 (1920).
(15) PEASE, D. C . , AND BLINKS,L. R . : J. Phys. Chem. 61, 556 (1947).
(16) PLAXTE, E . C., A N D SUTHERLASD, K. L. : J. Phys. Chem. 48, 203 (1943).
17) R A M S E Y , A. S.:A Treatise o n Hydromechanics. P a r t 11. Hydrodynamics, p. 160.
G. Bell and Sons, London (1935).
(18) SCHUHYASN, R., JR.:J. Phys. Chem. 46, 891 (1942).
(19) SIEDLER, P., hfOELLER, 8., AND REDDESHASE, T.: Kolloid-Z. 60, 320 (1932).
(20) S V E N - N I L S O K , I.: Ing. Vetenskaps Akad. Handl. No. 133 (1935).
(21) TAGGART, A. F.: Handbook of Ore Dressing. John \%ley and Sons, Inc., New York.
1927 edition, pp. 797-9, 806-8; 1945 edition, Section 12, pp. 52-4.
(22) VOLKOVA, Z.: Acta Physicochim. U.R.S.S. 20, 467 (1945).
(23) VOLKOVA, Z.: Acta Physicochim. U.R.S.S. 21, 171 (1946).
 VAPOR PHEjSURE-TEIIPER1TURE RELATIOSSHIPS 425

(24) T - o ~ ~ o vZ.:
a , Acta Physicochim. U.R.S.S. 21, 563 (1946).
(25) WARK,I. IT.: J. Phys. Chem. 40, 663 (1936).
(26) WARK, I. W.:J. Phys. Chem. 37, 639 (1933).
(27) DE KITT, C. C.: J. Am. Chem. Soc. 57, 775 (1935).
(28) Z ~ X I G AH.
, G. : Bol. minero soc. nacl. mineria (Santiago, Chile) 47, 83 (1935); Chem.
Abstracts 30, 75116 (1936).

Y=1POR PRESSLRE-TE1\IPERA4TURE RELhTIOSSHIPS A M O S G

T H E BR-4SCHED PAR-kFFIS HTDROC-4RBOKS
HARRY WIEKER
Department of Chemistry, Brooklyn College, Brooklyn, Mew Yo&
Receixed July 24, 1947
ISTRODCCTIOS
The difference in normal boiling point betn-een a branched-chain paraffin and
its straight-chain isomer can be expressed (4) as a function of two structural
variables by the equation'
98
At = - AW f 5.5Ap
n2
In this paper, it is shon-n that the boiling points of branched-chain paraffins
also obey this law a t pressures other than 7GO mm. of mercury, with only the
empirical constants changed.
In any equation relating the vapor pressures and temperatures of paraffins,
the constants involved \Till differ for individual isomers, and are therefore func-
tions of molecular structure. If the boiling points of isomeric paraffins at dif-
ferent pressures are linear functions of the strirctural parameters I w and A p ,
it is probable that the constants of temperature-pressure equations will be
represented by similar functions of these til-o variables. For the ,Intohe vapor-
pressure equation this rule holds, and the constants can be correlated by such
functions.
BOILISG POISTS .1T DIFFERCST PRESSURES
The general form of equation 1, a t pressures other than TGO mm. of mercury,
is
A! = - AW
k
n2
+ bAp
For a single group of isomers tz is constant, and equation 2 hecomes
It = alu: + hIp (3)
w is the sum of the distances, in terms of carbon-carbon bonds, betxeen the members
of all pairs of carbon atoms in the molecule; p is t h e number of pairs of carbon atoms sepa-
rated by three bonds; I t = f , - t,,,; l i o = zcn - tulso;I p = p n - p l s 0 .