Plan on working with HF? A friend who was president of an HF manufacturing company once gave me some valuable advice. He said there are several things to do before the plastic bottle of HF arrives. First, have a well ventilated fume hood available. Next, read up on HF first aid. Try to identify a hospital ER that could cope with an HF incident. How do you do that? You call and ask questions. Get some calcium gluconate salve. Learn what to do with it. If you have an incident, you will need to get decontaminated before you arrive at the hospital, otherwise there may be delays in getting teatment by the medical staff.
Here is my personal policy. You follow your own policies. If you handle HF and do not have a specific response plan, get one in place. If you handle this acid, you need to have a plan.
Do not rely on the local fire department to know what to do. They’ll want to take charge as soon as they arrive. Time will be lost as they ignore the staff of chemical experts standing right there while they confer on a plan. I’ve seen variants of this many times. It might transpire that the firemen will be ordered to stand clear of you until their commander has a plan for dealing with the contamination. So there you’ll sit.
Your main concern in a major splash incident is to get decontaminated. Your lab buddies who are there with you need to know how help you with this so there is no delay in getting you decontaminated. Do not wait for the fire department to come decontaminate you. Strip off contaminated clothing and get under the shower pronto, even if you have to use your one good arm to drag yourself there.
HF is a weak acid with a pKa of 3.17. It is somewhat skin permeable and will cause deep tissue injury. In addition to the general hydrolytic havoc associated with an acid exposure, HF delivers fluoride which scavenges calcium and will precipitate calcium fluoride in your tissues. That is what sets an HF exposure apart. This link to Honeywell Specialty Materials is especially well written and informative.
Avoid inhalation exposure and provide for splash protection. If you are heating it, consider using a full face respirator with appropriate cartridges when opening the sash of the hood when handling the reaction mixture. Wear a long rubber or plastic gloves and apron and make sure that your lab coat is non-absorbant. Be fastidious.
Don’t be afraid of HF. It is a lot like a table saw. You just have to know how to behave around it. And like a table saw, it’ll take body parts or worse from the careless or the complacent. You have to handle it carefully every single time. Be in the moment. Don’t get distracted by talkative bystanders. Pay attention to what you’re doing.
Lamentations on Chemistry 
I have worked in a lab with HF and our first safety rule for working with it was to never touch a vessel with HF in it while alone. We worked with elemental fluorine but it was the HF that we obsessed about. Everything that you say about emergency services is true, we had a grad student lose a significant part of her upper leg to an HF burn when a glass vessel broke. It was tragic from the time of the spill to the recovery.
I completely agree with @liberal chemist, when we worked with HF in my old lab, there was always someone standing nearby (doing nothing else but waiting to help you). This may sound silly, but it is well worth it having this safety precaution when working with HF
We had a process where we were using anhydrous HF on a ton cylinder scale in a reactor train @ 300 C/250 psi (nice!). The main issue was finding valves that could handle the pressure/temperature combination. Many vendors claimed to be able to have the proper MOC to handle this, but none were found, so the process was changed to avoid valves. The issue today is if you have more than a certain amount, Homeland Security becomes very interested in your facility and there are many, many pages of paperwork to fill out. We still use HF occasionally, but not at the temp/pressure combinations above.
The MOC thing is a real problem. Had the same issue with Cl2. Those $1100 Monel regulators are basically disposable. You’re experience with this wildly overshadows mine.
Wait, why was she working with HF in a glass vessel? (I don’t mean to be flippant– that is a serious tragedy. HF reactions require plastic flasks)
I work with aqueous HF on a daily basis. Our lab has a dedicated hood for HF work, and only one reaction at a time is permitted. In addition to the calcium gluconate salve, we have these additional precautions:
– We keep a squeeze bottle of saturated calcium chloride in the hood as the first option in neutralizing non-personal spills or excess HF. This helps rule out any uncertainty if you’re worried about contamination (sometimes it’s just paranoia)
– As well, we keep large volumes of zephiran (benzalkonium chloride aqueous solution) at hand in case the exposure is larger than a few drops. Immersing in an iced zephiran solution is a faster way of dealing with a spill than rubbing in the gluconate salve.
– Everyone in the lab (not just the people working with HF) is familiar with how HF is handled, and the safety steps to take in the event of exposure. Make sure you apply the salve while wearing gloves so you don’t further contaminate your hand!
I would *definitely* consider wearing a respirator if dealing with the possibility of gaseous HF.
Wow. I’m really glad you left this advice. I had’t thought about the CaCl2 or the benzalkonium chloride solution. This post is getting some traffic. Your comments will be seen by many others.
I appreciate any reply from anyone as to precautions one should take while handling Pyridine-HF complex. While I am always careful, I am curious if the protocol for Py-HF is same as HF alone. Thanks
Hydrofluorosilicic acid isn’t nearly as bad, but it’s still very nasty stuff, and water treatment plants work with it all the time, especially the bigger ones. These are water treatment plant oeprators, not necessarily trained chemists. Don’t even get me started on a rant about the un-necessity and ill-advisibility of fluoridating drinking water. I have a garage-full of papers on the topic. Biggest sacred cow in public health protection. And this isn’t even my rant! Yet.
Oh, I would dearly love to hear this. Oh, do tell!!
As you’ve said to me: It’ll cost you a beer. And it nearly cost me a job once. Easier to say than type, and everso much more entertaining for all!
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