PMID- 25137437
OWN - NLM
STAT- MEDLINE
DCOM- 20150602
LR  - 20161125
IS  - 1520-5207 (Electronic)
IS  - 1520-5207 (Linking)
VI  - 118
IP  - 36
DP  - 2014 Sep 11
TI  - Understanding solvation in the low global warming hydrofluoroolefin HFO-1234ze 
      propellant.
PG  - 10675-87
LID - 10.1021/jp5059319 [doi]
AB  - Hydrofluoroolefins (HFOs), with zero ozone-depleting effect and very low global 
      warming potential, are considered to be the next-generation high-pressure working 
      fluids. They have industrial relevance in areas including refrigeration and 
      medical aerosols. One major challenge expected in the replacement of existing 
      working fluids with HFOs is the solubility and solvation of additives in such 
      hydrophobic and oleophobic low dielectric semifluorinated solvents. The study of 
      the solvation of chemistries that represent those additives by HFOs is, 
      therefore, of great relevance. In this work, we systematically investigate how 
      the polarity and structure of fragments (the tail, t) that represent those 
      additives affect their binding energy (Eb) with HFO-1234ze 
      (1,1,1,3-tetrafluoropropene) (the solvent, s; Eb(st)). We also compare and 
      contrast those results with those for the working fluids that are most widely 
      used in the industry, the hydrofluoroalkanes (HFAs) HFA-134a and HFA-227. Three 
      main chemistries were investigated: alkanes, ethers, and esters. It was found 
      that HFO-1234ze interacts quite favorably with ethers and esters, as indicated by 
      their Eb(st), while Eb(st) with alkanes was much lower. While ether and ester 
      groups showed little difference in Eb(st), the much lower self-interaction energy 
      between ether tail-tail fragments (Eb(tt)) is expected to result in improved 
      solubility/solvation of those groups in HFO-1234ze when compared with the more 
      polar ester groups. The ratio Eb(st)/Eb(tt) is defined as the enhancement factor 
      (Eenh) and is expected to be a better predictor of solubility/solvation of the 
      tail fragments. The branching of the tail groups upon the addition of pendant CH3 
      groups did not significantly affect the solvation by the propellant. At low 
      branching density (one CH3 pendant group), it did not affect tail-tail 
      self-interaction either. However, at high enough branching (two CH3 groups), 
      steric hindrance caused a significant decrease in Eb(tt) and thus an increase in 
      Eenh, suggesting that branching may be used as a strategy to enhance solvation in 
      HFO propellants. Finally, the solvation behavior of HFO-1234ze was found to be 
      similar to that of HFA-134a, thus suggesting similar considerations may apply for 
      both propellants, when solvation properties are of a concern to the application.
FAU - Yang, Lin
AU  - Yang L
AD  - Department of Chemical Engineering and Materials Science, College of Engineering, 
      Wayne State University , 5050 Anthony Wayne Drive, Detroit, Michigan 48202, 
      United States.
FAU - da Rocha, Sandro R P
AU  - da Rocha SR
LA  - eng
PT  - Comparative Study
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
PT  - Research Support, U.S. Gov't, Non-P.H.S.
DEP - 20140902
PL  - United States
TA  - J Phys Chem B
JT  - The journal of physical chemistry. B
JID - 101157530
RN  - 0 (1,3,3,3-tetrafluoropropene)
RN  - 0 (Alkanes)
RN  - 0 (Esters)
RN  - 0 (Ethers)
RN  - 0 (Fluorocarbons)
RN  - 0 (Hydrocarbons, Fluorinated)
RN  - 0 (Solvents)
RN  - R40P36GDK6 (apaflurane)
SB  - IM
MH  - Alkanes/*chemistry
MH  - Esters/*chemistry
MH  - Ethers/*chemistry
MH  - Fluorocarbons/*chemistry
MH  - Hydrocarbons, Fluorinated/chemistry
MH  - Molecular Structure
MH  - Solubility
MH  - Solvents/*chemistry
MH  - Static Electricity
EDAT- 2014/08/20 06:00
MHDA- 2015/06/03 06:00
CRDT- 2014/08/20 06:00
PHST- 2014/08/20 06:00 [entrez]
PHST- 2014/08/20 06:00 [pubmed]
PHST- 2015/06/03 06:00 [medline]
AID - 10.1021/jp5059319 [doi]
PST - ppublish
SO  - J Phys Chem B. 2014 Sep 11;118(36):10675-87. doi: 10.1021/jp5059319. Epub 2014 
      Sep 2.