Unlocking the Secret Refrigerant Numbering Code

I have wondered why the new HFO refrigerant numbers look like an internet password. In short, the numbering system describes the chemical makeup of the refrigerant. But that is also true of the much simpler numbers, such as HCFC 22. So why does HFO 1233zd(E) look like a secret code? Mainly because the chemical is a bit more complicated. HFC 22 is a methane based molecule, with only one carbon. All that is needed to describe it is a way to determine how many fluorine, chlorine, and hydrogen atoms surround the single carbon atom. There is really only one way to put the molecule together.

HFO refrigerants are decidedly more complicated. They are built around a propene molecule. Propene has three carbon atoms surrounded by hydrogen atoms. Propene is similar to propane, except propane has all single bonds between its atoms while propene has a double bond between two of the carbons atoms.

You can think of each carbon atom as having four Velcro hooks. Molecules like propane only use 1 hook for each bond. This allows each carbon to bond to the most possible other atoms. Molecules constructed this way are referred to as saturated.  Two of the carbon atoms in a propene molecule use two Velcro straps to bond to each other, which reduces the number of other atoms the carbon molecules can bond with. Molecules built this way are referred to as unsaturated.

To unlock the secret code which describes fluorinated hydrocarbon refrigerants, just add 90 to the number, leaving off the leetrs for now. For example, 1233 + 90 = 1323. Working backwards from the right, the first number describes the number of fluorine atoms. In this case it is 3. The second number from the right describes the number of hydrogen atoms. In this case 2. The third number from the right describes the number of carbon atoms. In this case 3. The fourth number from the right lists the number of double bonds in the molecule. In this case 1. Notice the number of chlorine atoms was not addressed. The number of chlorine atoms is found by subtracting the fluorine and hydrogen atoms from the number of bonds. A propene molecule has 6 bonds. 6- 3 -2 = 1. There is one chlorine atom.

So what are the letters at the end of 1233zd(E)? The short answer is that all the letters following the number describe the particular molecular arrangement. We know that 1233zd(E) contains 3 carbons, 3 fluorines, 1 chlorine, and 2 hydrogens. However, even if you know exactly which atoms there are, you must also describe where they are attached because there are now many places to put them.

Each different arrangement of the same atoms produces different properties, so it is important to specify which arrangement the refrigerant is using. These different arrangements are called isomers. The two lower case letters after the number describe the specific arrangement (isomer). But note that this refrigerant number has yet another upper case letter after the two lower case letters. Some isomers have the same arrangement, but differ in spatial orientation. The upper case letter identifies which spatial orientation.

This is about as deep as I feel I should go in a blog post (maybe even a bit too deep). If you want more detail, it is all explained in the ASHRAE Standard 34-2016.

What is an HFO?

Hydrofluoroolefins, HFOs, are a relatively new class of low global warming potential refrigerants. They are actually composed of the same chemicals found in an HFC: hydrogen, fluorine, and carbon. If you define an HFC as a chemical containing those three elements, then HFOs are actually HFCs. The difference is in how they are constructed.

Ethane

HFC 134a

 Both HFCs and HFOs start out as a hydrocarbon, containing a chain of carbon atoms surrounded by hydrogen atoms. To make a traditional HFC you replace some of the hydrogen atoms with fluorine atoms. Standard hydrocarbon molecules and traditional HFC molecules are composed exclusively of single atomic bonds. You can think of an atomic bond as a type of Velcro strip holding the atoms together. Carbon has four atomic Velcro strips while hydrogen and fluorine just have one. Single bonds just attach one strip between atoms. Using only single bonds a carbon atom will connect to four other atoms because it has four bonds. Molecules constructed this way are called saturated. They have the maximum number of atoms joined together.

Propane

HFO 1234yf

What makes HFOs different is that they use a double bond between two carbon atoms. These two caron atoms are connected together with two Velcro strips instead of just one. Since carbon atoms only have four connections, using two to connect to each other means that each carbon can only connect to two other atoms besides each other. This reduces the total number of atoms that can be connected together. This type of molecular construction is called unsaturated.

Why does this make a difference? Unsaturated molecules are far less chemically stable and tend to break down easier. Since HFOs are less chemically stable, they do not survive long in the atmosphere – and so they do far less harm than the more stable saturated HFCs. The difference is dramatic. HFC 134a has a GWP of 1430 while HFO-1234yf has a GWP of 4.

However, HFOs have a design challenge to overcome: they are mildly flammable. The very instability that reduces their GWP increases their flammability. At present, building codes in the US generally do not recognize a difference between highly flammable refrigerants and mildly flammable ones. Most building codes do not allow the use of significant amounts of flammable refrigerant inside the building. ASHRAE is working on revising their Safety Standard for Refrigeration Systems,  Standard 15. It is projected to be ready by January 2018. For more information on the work being done on flammable refrigerants check out this article in Contracting Business
http://contractingbusiness.com/refrigeration/codes-preparing-technology-refrigerant-changes