Chromatography Forum

Does anybody have experience with quantifying TiCl4 by capillary GC. I only found old literature using packed columns.

What historical information have you found? Do you think it is reliable?

Do you not think it 'transfers' to capillary columns? Please share what you have even it no one has more modern information. It is a rather obscure topic and one that may not arise in the future.

Thanks.

Rod

Use of gas chromatography for the analysis of inorganic compounds. Agliulov, N. Kh.; Zelyaev, I. A.; Zueva, M. V.; Luchinkin, V. V.; Nikolaeva, L. G.; Feshchenko, I. A. USSR. Trudy po Khimii i Khimicheskoi Tekhnologii (1973), (3), 66-8.
Abstract
Gas chromatog. detns. are described for HCl > 10-3, Cl 3  10-6, CoCl2 2  10-6, SiCl4 4  10-6, and CCl4 2  10-6% in BCl3 (column length 4.4 m, temp. 60); HCl 5  10-3, SiCl4 2  10-4, and SiMeCl3 6  10-4% in SiHCl3 (2.5 m, 40); HCl 0.35 and SiHCl3 0.5% in SiCl4 (6m, 50); SiCl4 5  10-5, PCl3, 10-5, and AsCl3 10-4% in GeCl4 (3.5 m, 105); HCl 0.01%, Cl 3  10-4%, COCl2 2  10-4%, SiCl4 4  10-4%, and 7  10-5% in TiCl4 (4.4 m, 60); and SiCl4 0.01% and AsCl3 0.1% in GaCl3 (4 m, 80). The glass column was filled with 10-15% of the polymethylsiloxane PMS-20, PMS-100, or PMS-200 on Spherochrome 1. N was the carrier gas. A thermal cond. detector was used in the anal. of SiCl4 and GaCl3; in the other case a thermionic detector was used.



Elution characteristics of volatile chlorides in gas-liquid chromatography. Vranti Piscou, D.; Kontoyannakos, J.; Parissakis, G. Inorg. Anal. Chem. Lab., Natl. Tech. Univ. Athens, Athens, Greece. Journal of Chromatographic Science (1971), 9(8), 499-501.
Abstract
The elution characteristics of TiCl4, CCl4, SiCl4, GeCl4, SnCl4, PCl3, POCl3, and AsCl3 on 6 org. liq. phases are reported. The combination of thermodynamic and retention data provides useful material concerning the use of org. liq. phases in the field of inorg. gas chromatog. to the question of solute-solvent interactions.



Gas chromatography of inorganic volatile chlorides. Their reactivity towards certain column packing materials. Parissakis, G.; Vranti-Piscou, D.; Kontoyannakos, J. Inorg. Chem. Lab., Natl. Tech. Univ., Athens, Greece. Journal of Chromatography (1970), 52(3), 461-8.
Abstract
The volatile chlorides: CCl4, AsCl3, SiCl4, POCl3, PCl3, SnCl4, GeCl4, TiCl4, were sepd. and detd. under anhyd. conditions and by using the stationary partitioning phases; Kel-F oil 10, Apiezon L, Kel-F wax, Phasepak P, Silicone Rubber UC-W98, Silicone oil DC-550, and graphite in glass columns with a thermal cond. detector. SbCl5 and VCl4 could not be detd. because they interacted with the stationary phases to form unidentified peaks.

5% Fluorocol on 60/80 Graphitized Carbon Black would be a packing that should give you simlar results to the literature. I would use a fused silica coated SS tubing or glass tubing instead of nickel alloy tubing.

Alternately, a thick film methyl silicone capillary would be another alternative that might be possible.

Using an inert fiber to inject on column might be advised instead of a metal syringe. A temperature programmable injector also makes sense to me.

Good luck,

Rodney George

Thanks Rod!

We may test a DB-1 as we have to separate TiCL4 from some aliphatic and aromatic hydrocarbons, which we maybe also want to quantify.

Are there other, QC-suitable options for detection of these substances, than TCD or AED (will unfortunately be too expensive)?

I was quickly (google) searching for inert (metal-free) syringes for on-column injection without finding anything. Any ideas?

fused silica needles can be used when attached to a std syringe. See Hamilton or another supplier for their availability.

best wishes,

Rod

Alexst,

I'm curious if you had any luck with this analysis. Have you tried it yet?

AlexST,

I should think this is an application that would be very well served by an ECD. Certainly the TiCl4 would be very amenable to ECD just the same as SiCl4 is. Most of the other compounds mentioned in the abstracts have multiple chlorines as well.

It would mean you would shoot much less (some advantages and disadvantages to that idea) or put a big split right in front of the detector.

Best regards,

AICMM

Bricevan: no, we might need this in ~2years and I got no samples yet to play around.

AICMM: I also thought about a 2-deterctor set-up with ECD-FID, but maybe we will not analyse the aliphatic HCs and than I might succeed with an ECD alone. Another worry is that I generate HCl in the FID which will corrode it.

I´ll keep you updated, but maybe you´ll have to be quite patient.