CYANEX ® 272 Extractant

CYANEX 272 Extractant
CONTENTS
INTRODUCTION
Chemical Structure .............................................................................3 Typical Properties ...............................................................................3 Stability...............................................................................................3 Solubility Losses .................................................................................4 Toxicity ...............................................................................................4 Suitability of Construction Materials..................................................4
COBALT RECOVERY
Solvent Extraction Reagent

Selective for cobalt over nickel from sulfate and chloride media. Selective for zinc in the presence of calcium and cobalt. Extracts other metal cations.
Cobalt Nickel Selectivity .....................................................................5 Sulfate Solution (Table 1) ............................................................5 Chloride Solution (Table 2) ..........................................................5 Calcium Rejection...............................................................................6 Cobalt Extraction Isotherm.................................................................6 Cobalt Loading ...................................................................................6 Scrubbing Isotherm ............................................................................7 Stripping Isotherms ............................................................................7 Using H2SO4 (Table 7) .................................................................7 Using HCl (Table 8) ......................................................................7 Continuous Separation of Cobalt from Nickel in Sulfate Solution ..................................................................................7 Effect of Process Variables on Cobalt-Nickel Separation Factor ...............................................................................8 Effect of Temperature (Table 9) ...................................................9 Effect of Equilibrium pH (Table 10)..............................................9 Effect of Diluent Aromaticity (Table 11) ......................................9 Effect of Phase Modifier (Table 12) .............................................9
OTHER POTENTIAL APPLICATIONS

Diluent Oxidation and Prevention ....................................................10 Recovery from Ammoniacal Solutions (Table 13) ............................10 Extraction from Single Metal Sulfate Solutions (Table 14) .........................................................................10 Extraction from Single Metal Chloride Solutions (Table 15) .........................................................................11
ANALYTICAL METHODS
In Organic Solvents by Titration .......................................................13 In Organic Solvents by Gas Chromatography ..................................14 In Aqueous Solutions by Gas Chromatography ...............................15
HEALTH AND SAFETY..............................................15

INTRODUCTION
CYANEX 272 extractant has proven to be the reagent of choice for the separation of cobalt from nickel from both sulfate and chloride media. It is now being used to produce a major portion of the worlds cobalt. Since the active component of CYANEX 272 extractant is a phosphinic acid, metals are extracted through a cation exchange mechanism. Although CYANEX 272 extractant is selective for cobalt in the presence of nickel, a variety of other cations can also be extracted depending upon the solution pH. CYANEX 272 extractant is totally miscible with common aromatic and aliphatic diluents, and is extremely stable to both heat and hydrolysis.
Typical Properties
Bis(2,4,4-trimethylpentyl)phosphinic acid 85% Appearance Molecular Weight Specific Gravity at 24C Viscosity, Brookfield at 25C 50C Solubility in distilled H2O at pH 2.6 pH 3.7 Boiling Point Pour Point Flash Point, closed cup Specific Heat @ 52C Thermal Conductivity Colourless to light amber liquid 290 g/Mol 0.92 142cp 37cp 16 g/ml 38 g/mL >300C -32C >108C 0.48 cal/gm/C 2.7 x 10-4 cal/cm/sec/C
Chemical Structure
The active component of CYANEX 272 extractant is bis(2,4,4-trimethylpentyl)phosphinic acid.
Stability
The hydrolytic stability of CYANEX 272 extractant was examined in several tests which involved equilibrating the reagent with aqueous cobalt-nickel sulfate solutions at pH 5 and 50C. The experimental procedure involved contacting the aqueous and organic phases in a stirred vessel for one week and then stripping the organic phase with sulfuric acid. The solvent was subsequently returned to the vessel for a further one week contact with a fresh aqueous solution. The procedure was repeated for a total contact time of four weeks. Analysis by titration and 31P NMR failed to detect any degradation of the reagent, nor were any statistically significant changes in cobalt-nickel selectivity observed. Furthermore, no degradation has been detected in plants which have been operating continuously for as long as 25 years.

Suitability of Construction Materials
Metals: Samples of stainless steel (304 and 316), mild steel and aluminum in the form of coupons (approximate dimensions 50mm 1 x 20mm x 3mm) were immersed in capped jars for 8 /2 months at 50C (temperature was maintained only during working hours). No corrosion was observed in the three steel samples but aluminum exhibited minimal corrosion at a rate of 1 mil/year. Plastics and Rubbers: Samples of various plastics and rubbers were immersed in CYANEX 272 extractant and kept at 50C for a total of 424 hours. The following observations were made:
Solubility Losses
Losses of CYANEX 272 extractant by distribution to aqueous cobalt-nickel sulfate solutions were determined in a number of shake-out tests. The effect of two variables, pH and aqueous phase salt concentration, was studied. Aliquots of the organic and aqueous phases were contacted for 5 minutes at 50C and A/O = 1. After coalescence, the aqueous phases were analyzed for CYANEX 272 extractant using a gas chromatographic procedure. The solvent was composed of 12 v/o CYANEX 272 extractant in Kermac* 470B diluent. Ammonium hydroxide was used for pH adjustment. The results of the extractant solubility (truly dissolved data) are given below. Aqueous Composition (g/l) Ni Co Total Salt Conc. 100 25 2 25 300 133 Equilibrium pH 3-5 4.6 5.3 6.2 5 5 27 4.6 5.5 6.5 CYANEX 272 Extractant Solubility (g/ml) 0.5-1.5 2 2 2 3 8 25
Material
Butyl Rubber Teflon Fluorocarbon Film** Polypropylene Natural and Black Latex PVC Laboratory Grade PVC Solvent Grade Red Gum Rubber
Remarks
Unsuitable. Increase in dimensions and softening. Suitable. No measured effect. Suitable. No measured effect. Unsuitable. Complete dissolution in less than 192 hours. Short term suitability. Loss of plasticity in less than 192 hours. Suitable. Only small change in dimensions observed. Unsuitable. 100% increase in weight and dimensions and softening. Suitable. No measured effect. Unsuitable. Disintegrated after 56 hours. Unsuitable.
___________________________________________
The solubility losses follow the general pattern expected of an acidic extractant. Distribution to the aqueous phase was found to be proportional to pH and inversely proportional to salt concentration. As can be seen, the losses are not excessive and this is corroborated by operating plant experience where total annual losses from both solubility and entrainment are approximately 10-15% of the solvent inventory.
Toxicity
The acute oral (rat) and acute dermal (rabbit) LD50 values for CYANEX 272 extractant are >3.5 g/kg and >2.0 g/kg, respectively. The product produced only limited to mild eye and skin irritation during primary irritation studies with rabbits. The acute LC50, (96 hr) for the bluegill sunfish and rainbow trout are 46 mg/L and 22 mg/L, respectively. When CYANEX 272 extractant was assayed for mutagenic potential in the Ames Salmonella Test, it was determined to be non-mutagenic. CYANEX 272 extractant is considered as a non-toxic material.
* A product of Kerr McGee Refining Corp.
Viton Fluoroelastomer** Silicon EPDM

** Dupont Dow Elastomers
COBALT RECOVERY
Cobalt-Nickel Selectivity
The results of batch shake-out tests showing the effect of pH on Co-Ni selectivity from both sulfate and chloride media are given in Tables 1 and 2, respectively. TABLE 1 SULFATE SOLUTION Solvent (v/o) Aqueous (g/l) Temperature Contact Time A/O pH Control % Extraction Co Ni 21.5 0.04 43.7 0.08 88.0 0.37 96.7 1.05 100 1.81 12% CYANEX 272 extractant, 5% isodecanol in Kermac 470B diluent 1.96 Co, 98.0 Ni as sulfates 50C 5 minutes 1 NH4OH Equilibrium pH 3.8 4.2 5.3 5.7 6.1 Separation Factor 700 1000 2000 2700
TABLE 2 CHLORIDE SOLUTION Solvent (v/o) Aqueous (g/l) Temperature Contact Time A/O pH Control % Extraction Co Ni 2.9 0.1 54.2 0.3 98.1 7.0 99.7 30.0 99.9 72.9 10% CYANEX 272 extractant, 5% isodecanol in Kermac 470B diluent 0.88 Co, 1.76 Ni as chlorides 50C 5 minutes 1 NaOH Equilibrium pH 3.2 4.0 5.1 5.5 6.2 Separation Factor 40 370 680 680 650

TABLE 4 Solvent (v/o) Aqueous (g/1) Temperature Equilibrium pH pH Control 12% CYANEX 272 extractant, 5% isodecanol in Kermac 470B diluent. 5 Co as sulfate 50C 5.00.1 1N NaOH
Calcium Rejection
Unlike other organophosphorus cobalt extractants, CYANEX 272 extractant will extract cobalt preferentially to calcium when both are present in the same feed stream. This performance characteristic is demonstrated in Table 3 and Figure 1. TABLE 3 CALCIUM REJECTION IN THE PRESENCE OF COBALT AND NICKEL Solvent (v/o) Aqueous (g/1) Temperature Contact Time A/0 pH Control Co 3.1 17.2 54.3 91.7 98.3 100 FIgURE 1 % Extraction Ni 0 0.04 0.17 1.03 3.95 13.4 15% CYANEX 272 extractant, 10% p-nonylphenol in Kermac 470B diluent 1.60 Co, 77 Ni, 0.31 Ca as sulfates 50C 5 minutes 1 NH4OH Ca 0.95 1.24 3.33 12.0 25.7 5.16 Equilibrium pH 1.99 3.34 3.85 4.84 5.72 6.63
A/O 10 5 2 1
Equilibrium Cobalt Concentration (g/l) Solvent Aqueous 6.32 4.68 6.13 4.13 5.54 2.58 2.72 0.06
The actual loading capacity of this solvent was 6 g/l cobalt, whereas the stoichiometric capacity is approximately 10 g/l cobalt.
Cobalt Loading
Loading studies were carried out at 50C and pH 6.0 0.1. The pH was controlled by the addition of ammonia. Other details and results are shown in Table 5. TABLE 5 Solvent (v/o) Aqueous (g/l) Theoretical Maximum (g/l) Contact Time 30% CYANEX 272 extractant in Kermac 470B diluent 10 Co as sulfate Approximately 24 5 minutes % of Theoretical Maximum 21 42 63 96 96
A/O 0.5 1.0 1.5 3.0 5.0
Co in Solvent (g/l) 5 10 15 23* 23*
Cobalt Extraction Isotherm

Procedural details and results of our extraction studies are given in Table 4.
*At this loading the solvent was judged to be too viscous for practical use. The 15 g/l solvent did not exhibit this viscosity problem. The maximum practical loading for the conditions cited is probably about 65-75 % of theoretical. This would correspond to a CYANEX 272 extractant:cobalt ratio of 6:2.

It should be noted that the loading capacity of CYANEX 272 extractant will vary depending upon several parameters, notably pH, temperature, and extractant concentration, and may be more or less than the figure cited. For example, with a 15% CYANEX 272 extractant solution at 50C and pH 5-5 the solvent can be loaded to 100% of the theoretical maximum while remaining sufficiently mobile for practical use. TABLE 7 USINg H2SO4 Solvent (v/o) Solvent Loading (g/l) Temperature Contact Time Strip Feed (g/1) O/A 6.67 5 4 3.33 2.86 2
Scrubbing Isotherm
As can be seen from the results in Table 6, even if a high quantity of nickel is co extracted with the cobalt, it can be successfully scrubbed from the loaded solvent. TABLE 6 Solvent (v/o) Solvent Loading (g/1) Scrub Feed (g/1) Temperature 12% CYANEX 272 extractant, 5% isodecanol in Kermac 470B diluent 1.9 Co, 1.9 Ni 30 Co (as sulfate), initial pH 3.7 50C
12% CYANEX 272 extractant, 10% p-nonylphenol in Kermac 470B diluent 3.26 Co (2 g/ml Ni) 40C 5 minutes 20.5 Co (as sulfate), 24.5 H2SO4
Equilibrium Cobalt Conc. (g/l) Solvent Aqueous 0.58 38.4 0.22 35.7 0.19 32.5 0.03 31.3 0 29.8 0 27.0
TABLE 8 USINg HCl Solvent (v/o) 12% CYANEX 272 extractant, 10% p-nonylphenol in Kermac 470B diluent 9.26 Co 50C 5 minutes 19.4 Co (as chloride) 100 HCl
O/A 10 5 2 1
Equilibrium Concentration in Scrubbed Solvent (g/ml) Co Ni 3820 3790 3740 3730 4.5 2.2 1.3 1.1
Co-Ni Ratio 850 1720 2900 3400
Solvent Loading (g/1) Temperature Contact Time Strip Feed (g/1)
Stripping Isotherms
Stripping from a solvent modified with isodecanol tended to produce hazing. Substituting p nonylphenol or TBP for the isodecanol essentially eliminated this problem. Tables 7 and 8 show stripping isotherms obtained with a p-nonylphenol modified solvent.
O/A 2 3 5 7.5 10
Equilibrium Cobalt Conc. (g/l) Solvent Aqueous 0 37.9 0 47.1 0 65.7 0.01 88.8 0.35 108.5
Continuous Separation of Cobalt from Nickel in Sulfate Solution

In continuous countercurrent tests (four extraction and two scrub stages) carried out at Warren Spring Laboratory (Stevenage, U.K.), more than 99.5% of the cobalt in the feed was recovered as a product containing a Co-Ni ratio of greater than 1000 to 1.

Effect of Process Variables on Cobalt-Nickel Separation Factor
The effect of pH, temperature and diluent aromaticity on the cobalt-nickel separation factor in sulfate solutions was measured in a series of statistically designed tests and the data fitted to the following mathematical model: log10S = 1.8827 + 0.0332T + 0.01249A + 0.0033PT 0.002151PA - 0.0003405T2 Where: S = Co Ni Separation Factor T = Temperature (C) A = % Aromatics in diluent P = Equilibrium pH
The experimental conditions are shown below. A circuit flowsheet and the relevant assays are given in Figure 2. Solvent (v/o) 20% CYANEX 272 extractant (NH4 salt)*, 10% p-nonylphenol in the diluent MSB 210** 2 Co, 100 Ni as sulfates, 20 (NH4)2O4, pH 5 40 Co as sulfate, pH 3 50C Extraction A/O = 2 Scrubbing O/A = 32 Mixer Residence Time 3.5-4 minutes (Based upon total liquid flow)
Aqueous Feed (g/l) Scrub Feed (g/l) Temperature Phase Ratios
*The phosphinic acid contained in the solvent was converted 70% to the ammonium salt by reaction with concentrated ammonium hydroxide solution (S.G. = 0.88). A phase modifier was used since converting more than 50% of the free acid to a salt (NH4+ or Na+) usually requires a modifier to prevent third phase formation. ** A product of Shell Chemical Co.
FIgURE 2 CONTINUOUS TESTINg OF CyANEx 272 ExTRACTANT

The effect of these process variables on the separation factor is shown in Tables 9 through 11. TABLE 9 EFFECT OF TEMPERATURE Solvent (v/o) 22% CYANEX 272 extractant in the diluent (95% MSB 210* diluent, 5% Aromatic 150** diluent). 2 Co, 100 Ni as sulfates pH 5.5 A/O 1 Temperature C 30 35 40 45 50 55 60 TABLE 11 EFFECT OF DILUENT AROMATICITy Temperature Diluent (v/o) pH Other Conditions 50C 100% MSB 210 (aliphatic) to 100% Aromatic 150 5.5 See Table 9 Aromaticity v/o 0 10 20 30 40 50 60 70 80 90 100
Aqueous (g/l)
Co-Ni Separation Factor 3970 4030 4090 4160 4220 4280 4350 4420 4480 4550 4620
Co-Ni Separation Factor 1320 1850 2480 3220 4000 4790 5510
* A product of Shell Chemical Co. **A product of Exxon Co., USA.
TABLE 10 EFFECT OF EQUILIBRIUM pH Temperature Diluent (v/o) Other Conditions 50C 95% MSB 210, 5% Aromatic 150 See Table 9 pH 4.5 4.7 4.9 5.1 5.3 5.5
The effect of the phase modifiers TBP, p-nonylphenol, isodecanol and TOPO (tri-n-octylphosphine oxide) on the separation factor is shown in Table 12. TABLE 12 EFFECT OF PHASE MODIFIER Extractant (v/o) 22% 10 v/o (TBP, isodecanol, p-nonylphenol) 10 w/o TOPO (solid) 10 Co, 100 Ni as sulfates 1 55C 5.5 5 minutes MSB 210 Co-Ni Separation Factor 6700 3400 1800 1000 1000 Modifier
Co-Ni Separation Factor 2810 3010 3230 3470 3730 4000
Aqueous (g/l) A/O Temperature Equilibrium pH Contact Time Diluent
Modifier None TBP p-Nonylphenol Isodecanol TOPO
10 CYANEX 272 Extractant
OTHER POTENTIAL APPLICATIONS

Diluent Oxidation and Prevention
Hydrocarbon diluents oxidize readily to carboxylic acids in the presence of a cobalt (Co2+) catalyst. The formation of carboxylic acids, which are active nickel extractants, can seriously reduce the cobalt-nickel selectivity obtained with CYANEX 272 extractant. However, inhibitors such as BHT can be used to prevent this oxidation. Plants following this practice have run for many years without loss of selectivity. Although CYANEX 272 extractant is designed primarily for cobaltnickel separations, the data in Tables 14 and 15, and Figures 3 and 4 show that it will extract a variety of metal cations and indicate its potential for other selective separations. TABLE 14 ExTRACTION FROM SINgLE METAL SULFATE SOLUTIONS Solvent 0.6 M CYANEX 272 extractant, 10 v/o p-nonylphenol in Kermac 470B diluent Aqueous 0.015 M metal as sulfate Temperature 50C pH Control NH4OH or H2SO4 as appropriate Contact Time 5 minutes A/O 1
Recovery from Ammoniacal Solutions

CYANEX 272 extractant can be used to recover cobalt from ammoniacal as well as acidic solutions. The data in Table 13 show that it outperforms other organophosphorus extractants. TABLE 13 ExTRACTION FROM AMMONIACAL SOLUTIONS Solvent (v/o) Aqueous (g/L) Temperature pH Control Contact Time A/0 Extractant CYANEX 272 PC-88A D2EHPA 20% extractant, 5% isodecanol in Kermac 470B diluent 0.97 Co , 0.95 Ni , (NH4)2SO4 for a total SO42- concentration of 16 50C 11.6 with NH4OH 5 minutes 1 Co/Ni Separation Factor 58 18 7
3+ 2+
Metal Fe3+
Zn2+
% Extracted Co Ni 91.5 91.4 90.4 15.6 22.0 46.9
Cu
2+
Co2+
% Ext. Final pH 8.8 0.25 23.6 0.85 61.2 1.33 88.1 1.75 98.7 2.31 14.6 0.90 24.2 1.42 53.3 1.88 87.7 2.40 99.4 3.08 6.4 1.73 17.7 2.64 21.7 2.90 73.9 3.56 85.7 3.84 94.8 4.08 9.2 1.78 19.0 3.34 70.8 4.11 99.8 5.98 3.4 20.4 81.7 99.6 4.2 19.7 63.1 91.0 99.5 4.15 4.53 5.38 6.52 2.00 3.00 3.51 4.00 5.00
Metal % Ext. Final pH 27.6 6.33 36.0 6.59 2+ Ni 52.3 6.72 84.0 7.22 92.8 7.47 14.5 3.00 29.7 4.20 Mg2+ 67.1 4.76 82.0 4.99 97.4 5.81 23.9 1.11 41.9 2.50 3+ Al 87.5 2.92 97.2 3.14 42.3 86.1 99.8 7.9 21.1 46.5 85.1 3.40 3.96 5.66 1.11 1.34 1.44 1.81
Mn2+
Ca2+
V4+
Cd2+

TABLE 15 ExTRACTION FROM SINgLE METAL CHLORIDE SOLUTIONS Solvent Aqueous Temperature pH Control Contact Time A/O 0.6 M CYANEX 272 extractant in Exxsol D-80 0.015 M metal as chloride 50C NH4OH or HCl as appropriate 5 minutes 1
11
Metal
Ca2+
Co2+
Ni2+
Mg2+
% Ext. Final pH 0.0 3.33 25.7 4.36 48.9 5.00 91.9 5.90 99.4 6.45 1.9 2.8 48.0 3.5 86.7 4.1 95.9 4.4 100.0 5.5 0.0 3.6 19.3 4.9 44.7 5.2 84.8 5.9 95.1 6.3 99.7 7.0 1.2 3.4 41.2 4.4 66.2 5.0 89.1 5.4 99.0 6.4 99.9 6.6
Metal % Ext. Final pH 32.6 0.2 35.2 0.3 3+ Fe 66.4 0.7 95.2 1.1 99.0 1.4 0.0 2.0 8.5 2.6 2+ Cu 51.9 3.1 86.2 3.5 97.6 3.9 12.6 0.9 22.6 1.2 2+ Zn 54.2 1.6 67.9 1.7 76.2 1.8 92.9 2.1

Figure 3 Extraction of Metals by CyANEx 272 Extractant from Sulfate Solutions
Figure 4 Extraction of Metals by CyANEx 272 Extractant from Chloride Solutions
13
ANALYTICAL METHODS
Analysis for Active Component in CYANEX 272 Extractant in Organic Solvents by Titration
The active component of CYANEX 272 extractant is bis(2,4,4trimethylpentyl)phosphinic acid. Its concentration in an organic solvent is determined by titration with standard caustic solution. 4. Note the initial pH and begin to titrate with 0.1N NaOH. Record the pH as a function of the volume of NaOH added. Three endpoints should be observed. As each endpoint is approached, the incremental addition of NaOH should be reduced to 0.1 ml to facilitate calculation of the titer by the method of second differences.
Calculation
A typical potentiometric curve is as follows: The extractant contains small quantities of a dibasic impurity (2,4,4trimethylpentyl phosphonic acid) which also titrates with caustic.
The endpoints are detected potentiometrically.
Apparatus
pH meter Magnetic stirrer Standard laboratory glassware
Reagents
75 v/o 2-propanol in distilled water 0.1N Standard NaOH solution in 75 v/o 2-propanol 100 g/l H2SO4 All reagents are AR grade. The titer T1 corresponds to the neutralization of sulfuric acid dissolved in the solvent. T2 represents the neutralization of the phosphinic acid plus the reaction of the first of two replaceable hydrogen ions associated with the phosphonic acid. The phosphonic acid is totally neutralized at T3. 0.1N NaOH (ml) 9.8 9.9 10.0 10.1 10.2 10.3 pH 7.50 8.00 8.90 10.70 11.20 11.30 First Differential 50 90 180 50 10 Second Differential
Procedure
1. Contact approximately 50 ml of the solvent to be analyzed with 50 ml of 100 g/l H2SO4 for 5 minutes at 50C. Separate the phases and allow to stand for 15-30 minutes. Centrifuge the solvent or filter through PS paper* to remove entrained aqueous. 2. To prepare the analyte solution, pipette a 25 ml aliquot of the solvent and dilute to 200 ml in a volumetric flask with the appropriate diluent (Escaid**, Kermac*** etc.). Alternatively, the 75 v/o solution of 2-propanol may be used for volume make-up. 3. Pipette 25 ml of the analyte solution into a 150 ad tall-form beaker. Dilute to approximately 50 ml with the 2-propanol solution. Insert the pH electrodes and begin stirring.
* ** Phase separation paper available from Whatman Inc.,Clifton, NJ. A product of Exxon Chemical Co., USA
+40 +90 -130 -40
Then, T2 = (10.0 + 0.1)
*** A product of Kerr McGee Refining Corp.
x ____90___ 90 + 130
= 10.04 ml

T1 and T3 may be calculated in an analogous manner. When all three titers are known, the concentration of bis(2,4,4trimethylpentyl)phosphinic acid may be determined. bis(2,4,4-trimethylpentyl) phosphinic acid (g/1) = [T2 (T3 T2) T1] x N(NaOH) x 290 x 1000 1000 x 25 x 25 200 Similarly the concentration of the phosphonic acid and dissolved sulfuric acid may also be calculated. 2,4,4-trimethylpentyl phosphonic acid (g/1) = T3 T2 x N(NaOH) x 194 x 1000 1000 x 25 x 25 200 H2SO4 (g/l) = T1 x 49 x N(NaOH) x 1000 1000 x 25 x 25 200
Procedure
1. Pipette a 400 L aliquot of the organic phase and transfer it into a HP autosampler vial. Add 400 L of Methyl-8 Concentrate* (dimethylformamide dimethyl acetal) and 400 L of toluene. 2. Prepare standard solutions of CYANEX 272 extractant in toluene. 3. Pipette a 400 L aliquot of the standard solutions and transfer it into a HP autosampler vial. Add 400 L of Methyl-8 Concentrate and 400 L of toluene. 4. Analyze the methylated sample and standard solutions by gas chromatography as described under chromatographic conditions.
* A product of Pierce Co., USA
Chromatographic Conditions
Instrument: Hewlett-Packard 6890 50C 300C 310C 10C per minute 0 min. 10 min. 35 min. Split 300C 4.7 psi 10:1 68.9 mL/min 78.3 mL/min On 15.0 mL/min 2 min Helium J&W capillary column type DB-5 (5% phenyl-methylpolysiloxane) J&W J125-5032 DB-5 300C 30 m 540 m 1.50 m Constant flow 6.9 mL/min 4.7 psi 47 cm/sec
Oven Parameters
Initial Temperature: Final Temperature: Maximum Temperature: Rate: Initial Time: Final Time: Run Time:
Notes
1. A minimum net titer, i.e. [T2 (T3 T2) T1], of 10 ml is recommended to obtain reproducible results. In this procedure, 10 ml of 0.1N NaOH is equivalent to approximately 100 g/l concentration of phosphinic acid. Where necessary, the size of the aliquots and dilutions may be varied to ensure a sufficient volume of titrant is consumed. 2. Approximate pHs corresponding to the T1, T2 and T3 endpoints are 4, 9 and 11, respectively. However these values may vary depending upon the composition of the solvent. After gaining experience with a system, the NaOH may be added rapidly until the particular endpoint pH is approached and then added in 0.1 ml increments to define the point of inflexion in the curve. 3. The concentrations of sulfuric and phosphonic acids in the solvent are usually small and these endpoints may not be observed. In this case T1 and T3 should be assigned a value of zero in the calculations. Typically, T1 and T3 - T2) will be < 0.2 and < 0.1 ml of 0.1N NaOH, respectively, corresponding to <0.3 g/l H2SO4 and < 0.6 g/l phosphonic acid
Inlet Parameters
Mode: Initial Temperature: Pressure: Split Ratio: Split Flow: Total Flow: Gas Saver: Saver Flow: Saver Time: Gas Type:
Column Parameters
Type: Model Number: Maximum Temperature: Nominal Length: Nominal Diameter: Nominal Thickness: Mode: Initial Flow: Nominal Initial Pressure: Average Velocity:
Analysis for Active Component in CYANEX 272 Extractant in Organic Solvents by Gas Chromatography
The concentration of the active component, bis(2,4,4trimethylpentyl)phosphinic acid in the organic solvent is determined by gas chromatography of its methylate derivative.

Detector Parameters
Type Temperature Helium Flow Hydrogen Flow Air Flow Makeup Flow Makeup Gas Type Flame Ionization Detector (FID) 300C 8 mL/min 35 mL/min 400 mL/min 35 mL/min Helium
15
Health and Safety

The oral and dermal toxicity of CYANEX 272 extractant is low. CYANEX 272 extractant produces moderate eye and skin irritation upon contact. CYANEX 272 extractant did not produce an allergic dermal reaction in guinea pigs after repeated dermal exposure. This product did not produce mutations in bacteria. CYANEX 272 extractant is toxic to fish and invertebrates and care should be exercised to avoid environmental exposure.
Sample Injection
Volume Peak Areas 0.1 L Electronic integration. The compound has a retention time of about 17.8 minutes.
Technical reference list available upon request.
Analysis for Active Component in CYANEX 272 Extractant in Aqueous Solutions by Gas Chromatography
The concentration of the active component, bis(2,4,4trimethylpentyl)phosphinic acid in water is determined by gas chromatography of its methylated derivative.
Procedure
1. Transfer approximately 1 L of the aqueous solution into a plastic container and place it in a water bath set for 45C for a few hours. 2. Remove the solution from the water bath and allow to cool to room temperature. 3. From the bottom of the plastic container, dispense 600 g of the solution into a 1 L separatory funnel. 4. Add to the solution 5 mL of concentrated sulphuric acid, 50 mL of toluene and approximately 100 g of sodium chloride. 5. Separate both aqueous and organic phases. 6. Pipette a 1000 L aliquot of the organic phase and transfer it into a HP autosampler vial. Add 200 L of Methyl-8 Concentrate. 7. Prepare standard solutions of CYANEX 272 extractant in toluene. 8. Pipette a 1000 L aliquot of the standard solutions and transfer it into a HP autosampler vial. Add 200 L of Methyl-8 Concentrate. 9. Analyze the methylated sample and standard solutions by gas chromatography. The chromatographic conditions are identical to those previously described in the section Analysis for Active Component in CYANEX 272 Extractant in Organic Solvents by Gas Chromatography, except the volume injected by the GC autosampler is 1.0 L.
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Cytec Industries Inc. in its own name and on behalf of its affliated companies (collectively, Cytec) decline any liability with respect to the use made by anyone of the information contained herein. The information contained herein represents Cytecs best knowledge thereon without constituting any express or implied guarantee or warranty of any kind (including, but not limited to, regarding the accuracy, the completeness or relevance of the data set out herein). Cytec is the sole owner or authorized user of the intellectual property rights relating to the information communicated. The information relating to the use of the products is given for information purposes only. No guarantee or warranty is provided that the product is adapted for any specific use. The user or purchaser should perform its own tests to determine the suitability for a particular purpose. The final choice of use of a product remains the sole responsibility of the user. TRADEMARK NOTICE The indicates a Registered Trademark in the United States and the or * indicates a Trademark in the United States. The mark may also be registered, the subject of an application for registration or a trademark in other countries.
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