Dear Pier,

 

Thanks for your reply. I look forward to seeing the Chapter you mention. Is there any possibility that I could see a pre-publication copy?

 

My interest has been stirred by the results of some experiments that I have conducted on the effect of reaction temperature on the oxygen isotope composition of CO2 produced by the phosphoric acid reaction. After a little investigation of the “phosphoric” system it appears to me that the reaction is not between orthophosphoric acid and carbonate, but pyrophosphoric acid (for acids with nominal H3PO4 concentrations >90%). Since the reaction is exothermic I want to find out if there are any consequences for the accuracy of the reaction temperature. Intuitively I would expect that the reaction between “phosphoric” acid and carbonate at 25oC is so slow that any energy released by the reaction would be lost by conduction before it was able to increase significantly the temperature of the acid at the site of reaction. However, at high temperature the reaction is almost instantaneous and there seems the possibility that the energy release might be sufficiently fast to increase the real reaction temperature. If temperature was increased by more than 1oC then this would start to have potentially significant consequences for estimates of analytical uncertainty. It is this effect that I wanted to investigate. Unfortunately my knowledge of the chemistry in insufficient to allow me to place quantitative estimates on the consequences with any confidence. I would be interested to know if this subject is covered in your chapter.

 

Regards,

 

Steve

 

Department of Earth & Ocean Sciences
University of Liverpool
4 Brownlow Street
Liverpool
L69 3GP
UK

0151 794 5163/5164

Remember:

"If there's anything that you want,
If there's anything that you need?
There's no need to be evasive,
Money talks, and it's persuasive."

Elvis Costello


From: Stable Isotope Geochemistry [mailto:[log in to unmask]] On Behalf Of Pier de Groot
Sent: 23 April 2008 11:53
To: [log in to unmask]
Subject: Re: Reaction of phosphoric acid with CaCO3

 

Dear Steve,

The acid digestion reaction of carbonates by phosphoric acid is more complicated than it looks like. Work has been done on this matter, sure. If you are a bit patient, second half of this year my handbook Vol-II will be available, where in the chapter on O- and C-isotopes in carbonates (Chapter 4-5) a detailed description is presented on properties of phosphoric acid (contributed to the chapter by Hilary Le Q Stuart-Williams), which will give some more understanding of this system. Certainly, description of this system cannot be done by just a simple thermodynamics calculation.

Not much of a help for now, but still I hope it gives some answer,
Best wishes,
Pier.
****************************************************************
Delta Isotopes Consultancy

Dr. Pier A. de Groot
Pastoor Moorkensstraat 16
2400 Mol - Achterbos
Belgium
Tel. +32 (0)14 326 205
e-mail: [log in to unmask] or [log in to unmask]

Associate editor for stable isotopes of eEarth on-line magazine
http://www.electronic-earth.net

Head of Isotopes in Geosciences of the European Geoscience Union (EGU).
EGU Home web-site: http://www.copernicus.org/EGU/EGU.html
Isotope program for the EGU2008 General Assemblee can be found at:
http://www.cosis.net/members/meetings/programme/view.php?m_id=49&p_id=316&PHPSESSID=1ad86b0d1b35d7bf9aee006f1e2f5cf4

Organization Committee member of BASIS (Benelux Association of Stable Isotope Scientists).
http://www.basis-online.eu/

Visit my WEB-site about my “Handbook of Stable Isotope Analytical Techniques”, with a link to the Elsevier web site on the handbook (marked: ‘Order Now’):
http://users.pandora.be/handbook/index.html
last update: August 15, 2005
Volume I is available. Volume II is in press and will be available second half of 2008.

****************************************************************


From: "Crowley, Stephen" <[log in to unmask]>
Reply-To: Stable Isotope Geochemistry <[log in to unmask]>
Date: Wed, 23 Apr 2008 09:49:27 +0100
To: <[log in to unmask]>
Conversation: Reaction of phosphoric acid with CaCO3
Subject: [ISOGEOCHEM] Reaction of phosphoric acid with CaCO3

Dear Colleagues,
 
I would like to investigate aspects of the thermodynamics of the reaction of CaCO3 with phosphoric acid. Unfortunately it has quickly become apparent that I lack the necessary expertise to evaluate this chemical system with any confidence. I wonder if anyone with a reasonable grasp of thermodynamics would be interested in discussing this?
 
If so, please contact me directly. I don’t want to bore 99.99% of ISOGEOCHEM users with this esoteric problem.
 
Regards,
 
Steve Crowley
 

Department of Earth & Ocean Sciences
University of Liverpool
4 Brownlow Street
Liverpool
L69 3GP
UK

0151 794 5163/5164