Electronic Supplementary Material (ESI) for Chemical Science. This journal is © The Royal Society of Chemistry 2017
Electronic Supplementary Information
What is the fundamental ion specific series for anions and cations? Ion specificity in standard partial molar volumes of electrolytes and electrostriction in water and non-aqueous solvents
Virginia Mazzinia and Vincent S. J. Craiga,∗ a
Department of Applied Mathematics, Research School of Physics and Engineering, The Australian National University, Canberra, ACT, 2601, Australia. ∗ corresponding author, E-mail:
[email protected]
Contents Tabulation of the volume values
S2
standard molar volumes of electrolytes protic solvents S7 aprotic solvents S8 electrostrictive volume of electrolytes protic solvents S10 aprotic solvents S11
S7
S10
normalised electrostrictive volume of electrolytes protic solvents S13 aprotic solvents S14
S13
Tabulation of the volume values Table S1 Values of all the volumes used in this paper
modea
− ◦
− ◦
minimum errorb V i el
electrolyte
solvent
RbF NaF CsOAc KF LiOAc LiF CsF NaCl NaBr KOAc KCl RbCl KBr NaOAc NaClO4 NaI CsCl RbBr CsI KI CsBr RbI KSCN NaSCN LiCl LiBr LiSCN RbClO4 CsClO4 LiI KClO4 LiClO4
water water water water water water water water water water water water water water water water water water water water water water water water water water water water water water water water
32.6 16.4 79.2 23.7 53.6 11.6 33.6 29.6 35.1 61 38 42.3 43.9 49.4 52.9 44.8 48.8 48.4 66.8 54 54.8 58.9 57.7 46.6 24.1 30.3 45.5 63.8 69.8 38.1 55.0 43.8
C M Cd M Cc M M M M S M M M S S M M M M M M M S Cf M M Ce C C M C C
12.9 −2.4 61.8 7.9 39.6 −2.0 20.2 16.6 23.5 49.5 26.9 31.9 33.7 39.3 42.9 35.0 39.2 38.8 57.6 45.2 46.1 50.3 49.6 39.4 17.0 23.8 39.7 58.2 65.5 35.3 53.1 43.2
R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R
−19.7 −18.8 −17.4 −15.8 −14.1 −13.6 −13.4 −13.0 −11.6 −11.5 −11.2 −10.4 −10.2 −10.2 −10.0 −9.8 −9.6 −9.6 −9.2 −8.8 −8.8 −8.6 −8.1 −7.2 −7.2 −6.5 −5.8 −5.6 −4.4 −2.8 −1.8 −0.6
−60.5 −114.5 −22.0 −66.8 −26.2 −117.6 −39.9 −43.9 −33.0 −18.9 −29.3 −24.6 −23.2 −20.5 −18.9 −21.9 −19.7 −19.9 −13.8 −16.2 −16.0 −14.6 −14.0 −15.5 −29.7 −21.4 −12.6 −8.7 −6.3 −7.2 −3.3 −1.3
RbF NaF CsI NaCl NaI RbI KI CsF LiF KF RbCl KCl NaClO4 NaBr CsCl KSCN NaSCN RbBr KBr CsBr
MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH
32.6 16.4 66.8 29.6 44.8 58.9 54 33.6 11.6 23.7 42.3 38 52.9 35.1 48.8 57.7 46.6 48.4 43.9 54.8
C M M M M M M M M M M M S M M S Cf M M M
−5 −20 33 −3.9 11.3 26 21.7 2 −20 −7.6 11 7 22 4.3 18 28 17 19 14.7 26
4 4 4 R R 4 R 4 4 R 4 R 4 R 4 4 4 4 R 4
−37.6 −36.4 −33.8 −33.5 −33.5 −32.9 −32.3 −31.6 −31.6 −31.3 −31.3 −31 −30.9 −30.8 −30.8 −29.7 −29.6 −29.4 −29.2 −28.8
−115.3 −222.0 −50.6 −113.2 −74.8 −55.9 −59.8 −94.0 −272.4 −132.1 −74.0 −81.6 −58.4 −87.7 −63.1 −51.5 −63.5 −60.7 −66.5 −52.6
V i intr
Vi
Volumes and error in cm3 mol−1 . M: from molten salts S1 ; S: from soluble salts S2 ; C: calculated from density of the crystal S3 ; recommended by the reviewer S4,S5 . c from Ref. S6; d Ref. S7; e Ref. S8; f Ref. S9.
a
S2
N(% electrostr)
b
“R” indicates a value
modea
− ◦
− ◦
minimum errorb V i el
electrolyte
solvent
V i intr
LiCl LiSCN LiI RbClO4 LiBr CsClO4 KClO4 LiClO4
MeOH MeOH MeOH MeOH MeOH MeOH MeOH MeOH
24.1 45.5 38.1 63.8 30.3 69.8 55.0 43.8
M Ce M C M C C C
−4.5 17 11 37 4 44 33 22
R 4 4 4 4 4 4 4
−28.6 −28.5 −27.1 −26.8 −26.3 −25.8 −22.0 −21.8
−118.7 −62.6 −71.1 −42.0 −86.8 −37.0 −40.0 −49.8
LiF RbF NaF KF LiBr CsF LiI LiOAc LiCl NaI KI RbI CsI NaBr KBr NaCl RbBr KCl CsBr RbCl CsOAc CsCl KOAc NaOAc
EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH EtOH
11.6 32.6 16.4 23.7 30.3 33.6 38.1 53.6 24.1 44.8 54 58.9 66.8 35.1 43.9 29.6 48.4 38 54.8 42.3 79.2 48.8 61 49.4
M C M M M M M Cc M M M M M M M M M M M M Cd M S S
−35 −8 −23 −14 −5.2 0 5 22 −4.9 16.2 25.5 32 40 9 18 5 24 14 32 20 57 28 43 34
4 4 4 4 R 4 4 4 R R R 4 4 4 4 4 4 4 4 4 4 4 4 4
−46.6 −40.6 −39.4 −37.7 −35.5 −33.6 −33.1 −31.6 −29 −28.6 −28.5 −26.9 −26.8 −26.1 −25.9 −24.6 −24.4 −24 −22.8 −22.3 −22.2 −20.8 −18 −15.4
−401.7 −124.5 −240.2 −159.1 −117.2 −100 −86.9 −59.0 −120.3 −63.8 −52.8 −45.7 −40.1 −74.4 −59.0 −83.1 −50.4 −63.2 −41.6 −52.7 −28.0 −42.6 −29.5 −31.2
RbF NaCl NaBr CsCl NaF KCl RbCl CsBr CsI LiF RbBr LiBr KBr NaI LiSCN LiCl RbI KF CsF KI KSCN NaClO4 NaSCN LiI
FA FA FA FA FA FA FA FA FA FA FA FA FA FA FA FA FA FA FA FA FA FA FA FA
32.6 29.6 35.1 48.8 16.4 38 42.3 54.8 66.8 11.6 48.4 30.3 43.9 44.8 45.5 24.1 58.9 23.7 33.6 54 57.7 52.9 46.6 38.1
C M M M M M M M M M M M M M Ce M M M M M S S Cf M
24 21.3 28.2 42.3 10 31.7 36 48.9 61 6 43 25 38.8 40 41 19.9 55 20 30 50.6 55 51 45 37
4 R R R 4 R 4 R 4 4 4 4 R R 4 R 4 4 4 R 4 4 4 4
−8.6 −8.3 −6.9 −6.5 −6.4 −6.3 −6.3 −5.9 −5.8 −5.6 −5.4 −5.3 −5.1 −4.8 −4.5 −4.2 −3.9 −3.7 −3.6 −3.4 −2.7 −1.9 −1.6 −1.1
−26.5 −28.0 −19.7 −13.3 −39.0 −16.6 −14.9 −10.8 −8.7 −48.3 −11.2 −17.5 −11.6 −10.7 −9.8 −17.4 −6.6 −15.6 −10.7 −6.3 −4.7 −3.6 −3.4 −2.9
Vi
Volumes and error in cm3 mol−1 . M: from molten salts S1 ; S: from soluble salts S2 ; C: calculated from density of the crystal S3 ; recommended by the reviewer S4,S5 . c from Ref. S6; d Ref. S7; e Ref. S8; f Ref. S9.
a
S3
N(% electrostr)
b
“R” indicates a value
− ◦
− ◦
N(% electrostr)
4 4 4 4
1.2 1.2 3.2 6.0
1.7 1.9 7.3 10.9
26 17 −3 2 11 20.9 22.2 30 16.4 26 46.5 27.6 36.7 38 36 43 33.2 62 45 52
R 4 4 4 4 R R 4 R 4 R R R 4 4 4 R 4 4 4
−32.9 −15.6 −14.6 −14.4 −12.7 −8.7 −8.1 −8 −7.7 −7.6 −7.5 −7.5 −7.2 −6.8 −6.3 −5.4 −4.9 −4.8 −3.8 −2.8
−55.9 −47.9 −125.9 −87.8 −53.6 −29.4 −26.7 −21.1 −32.0 −22.6 −13.9 −21.4 −16.4 −15.2 −14.9 −11.2 −12.9 −7.2 −7.8 −5.1
M M M M M M M M M M M M S M M M C C C C
7 50 33 14 27 23 15.3 44 39.5 24 31 43 41.5 37 24 33 61 55 37.1 51
4 4 4 4 4 4 R 4 R 4 4 4 R 4 4 4 4 4 R 4
−17.1 −16.8 −15.8 −15.6 −15.3 −15 −15 −14.9 −14.5 −14.1 −13.8 −11.8 −11.4 −11.4 −11.1 −10.9 −8.8 −8.8 −6.7 −4.0
−71.0 −25.1 −32.4 −52.7 −36.2 −39.5 −49.5 −25.3 −26.9 −37.0 −30.8 −21.5 −21.6 −23.6 −31.6 −24.8 −12.7 −13.7 −15.3 −7.2
54 38.1 52.9 43.8 44.8 55.0
M M S C M C
47 35 52 43 44 55
4 4 4 4 4 4
−7 −3.1 −0.9 −0.8 −0.8 0.0
−13.0 −8.1 −1.7 −1.9 −1.8 0.0
24.1 38 32.6 11.6 30.3
M M C M M
4.5 20 15 −6 13
R 4 4 4 4
−19.6 −18 −17.6 −17.6 −17.3
−81.3 −47.4 −54.1 −151.7 −57.1
modea
Vi
69.8 63.8 43.8 55.0
C C C C
71 65 47 61
EG EG EG EG EG EG EG EG EG EG EG EG EG EG EG EG EG EG EG EG
58.9 32.6 11.6 16.4 23.7 29.6 30.3 38 24.1 33.6 54 35.1 43.9 44.8 42.3 48.4 38.1 66.8 48.8 54.8
M C M M M M M M M M M M M M M M M M M M
LiCl CsI CsCl NaCl RbCl KCl LiBr RbI KI LiI NaI CsBr NaClO4 RbBr NaBr KBr CsClO4 RbClO4 LiClO4 KClO4
PC PC PC PC PC PC PC PC PC PC PC PC PC PC PC PC PC PC PC PC
24.1 66.8 48.8 29.6 42.3 38 30.3 58.9 54 38.1 44.8 54.8 52.9 48.4 35.1 43.9 69.8 63.8 43.8 55.0
KI LiI NaClO4 LiClO4 NaI KClO4
EC EC EC EC EC EC
LiCl KCl RbF LiF LiBr
DMSO DMSO DMSO DMSO DMSO
electrolyte
solvent
CsClO4 RbClO4 LiClO4 KClO4
FA FA FA FA
RbI RbF LiF NaF KF NaCl LiBr KCl LiCl CsF KI NaBr KBr NaI RbCl RbBr LiI CsI CsCl CsBr
V i intr
minimum errorb V i el
Volumes and error in cm3 mol−1 . M: from molten salts S1 ; S: from soluble salts S2 ; C: calculated from density of the crystal S3 ; recommended by the reviewer S4,S5 . c from Ref. S6; d Ref. S7; e Ref. S8; f Ref. S9.
a
S4
b
“R” indicates a value
− ◦
modea
Vi
29.6 48.8 42.3 35.1 43.9 16.4 48.4 54.8 23.7 33.6 66.8 54 38.1 44.8 58.9 52.9 69.8 43.8 63.8 55.0
M M M M M M M M M M M M M M M S C C C C
12.5 32 26 19.5 28.4 1 33 39.8 9 21 54.2 42.2 27 33.7 48.2 47 67 41 61 55
ACE ACE ACE ACE ACE ACE ACE ACE
24.1 43.8 38.1 30.3 29.6 52.9 44.8 35.1
M C M M M S M M
RbCl CsCl RbBr KCl CsBr NaCl KBr NaBr LiCl RbI NaI CsI LiBr KSCN KI LiSCN NaClO4 RbClO4 CsClO4 NaSCN LiI KClO4 LiClO4
MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN
42.3 48.8 48.4 38 54.8 29.6 43.9 35.1 24.1 58.9 44.8 66.8 30.3 57.7 54 45.5 52.9 63.8 69.8 46.6 38.1 55.0 43.8
CsI LiBr CsBr LiSCN
NMF NMF NMF NMF
66.8 30.3 54.8 45.5
electrolyte
solvent
V i intr
NaCl CsCl RbCl NaBr KBr NaF RbBr CsBr KF CsF CsI KI LiI NaI RbI NaClO4 CsClO4 LiClO4 RbClO4 KClO4
DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO
LiCl LiClO4 LiI LiBr NaCl NaClO4 NaI NaBr
− ◦
minimum errorb V i el
N(% electrostr)
R 4 4 R R 4 R R 4 4 R R 4 R R 4 4 4 4 4
−17.1 −16.8 −16.3 −15.6 −15.5 −15.4 −15.4 −15 −14.7 −12.6 −12.6 −11.8 −11.1 −11.1 −10.7 −5.9 −2.8 −2.8 −2.8 0.0
−57.8 −34.4 −38.5 −44.4 −35.3 −93.9 −31.8 −27.4 −62.0 −37.5 −18.9 −21.9 −29.1 −24.8 −18.2 −11.2 −4.1 −6.4 −4.3 0.0
−70 −42 −31 −37 −26 2 13 7
4 4 4 4 4 4 4 4
−94.1 −85.8 −69.1 −67.3 −55.6 −50.9 −31.8 −28.1
−390.5 −195.8 −181.4 −222.1 −187.8 −96.2 −71.0 −80.1
M M M M M M M M M M M M M S M Ce S C C Cf M C C
−3 4 4 −6 11 −14 1 −7 −17 18.3 4.3 26.4 −10 18.7 15.7 9 17 28 35 12 5 25 15.3
4 4 4 4 4 4 4 4 4 R R R 4 R R 4 4 4 4 4 4 4 R
−45.3 −44.8 −44.4 −44 −43.8 −43.6 −42.9 −42.1 −41.1 −40.6 −40.5 −40.4 −40.3 −39 −38.3 −36.5 −35.9 −35.8 −34.8 −34.6 −33.1 −30.0 −28.5
−107.1 −91.8 −91.7 −115.8 −79.9 −147.3 −97.7 −119.9 −170.5 −68.9 −90.4 −60.5 −133.0 −67.6 −70.9 −80.2 −67.9 −56.1 −49.9 −74.2 −86.9 −54.5 −65.1
M M M Ce
55 18.7 44 36
4 R 4 4
−11.8 −11.6 −10.8 −9.5
−17.7 −38.3 −19.7 −20.8
Volumes and error in cm3 mol−1 . M: from molten salts S1 ; S: from soluble salts S2 ; C: calculated from density of the crystal S3 ; recommended by the reviewer S4,S5 . c from Ref. S6; d Ref. S7; e Ref. S8; f Ref. S9.
a
S5
b
“R” indicates a value
electrolyte
solvent
KBr CsCl KI NaBr NaI LiI KCl NaCl LiCl KSCN NaClO4 CsClO4 LiClO4 NaSCN KClO4
NMF NMF NMF NMF NMF NMF NMF NMF NMF NMF NMF NMF NMF NMF NMF
LiBr RbBr RbCl KBr KCl CsBr CsCl NaCl LiCl NaBr CsI RbI KI NaI LiI NaClO4 RbClO4 CsClO4 LiClO4 KClO4
DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF DMF
− ◦
− ◦
modea
Vi
43.9 48.8 54 35.1 44.8 38.1 38 29.6 24.1 57.7 52.9 69.8 43.8 46.6 55.0
M M M M M M M M M S S C C Cf C
35 40 45.5 27.1 37.3 31 31 22.7 17.3 51 47 64 40 43 55
4 4 R R R 4 4 R R 4 4 4 4 4 4
−8.9 −8.8 −8.5 −8 −7.5 −7.1 −7 −6.9 −6.8 −6.7 −5.9 −5.8 −3.8 −3.6 0.0
−20.3 −18.0 −15.7 −22.8 −16.7 −18.6 −18.4 −23.3 −28.2 −11.6 −11.2 −8.4 −8.7 −7.7 0.0
30.3 48.4 42.3 43.9 38 54.8 48.8 29.6 24.1 35.1 66.8 58.9 54 44.8 38.1 52.9 63.8 69.8 43.8 55.0
M M M M M M M M M M M M M M M S C C C C
0.2 19 13 14.9 9 26 20 1 −3.8 7.3 40.7 34.6 31.3 22.2 16 33 45 52 27 41
R 4 4 R 4 4 4 4 R R R R R R 4 4 4 4 4 4
−30.1 −29.4 −29.3 −29 −29 −28.8 −28.8 −28.6 −27.9 −27.8 −26.1 −24.3 −22.7 −22.6 −22.1 −19.9 −18.8 −17.8 −16.8 −14.0
−99.3 −60.7 −69.3 −66.1 −76.3 −52.6 −59.0 −96.6 −115.8 −79.2 −39.1 −41.3 −42.0 −50.4 −58.0 −37.6 −29.4 −25.5 −38.4 −25.4
V i intr
minimum errorb V i el
Volumes and error in cm3 mol−1 . M: from molten salts S1 ; S: from soluble salts S2 ; C: calculated from density of the crystal S3 ; recommended by the reviewer S4,S5 . c from Ref. S6; d Ref. S7; e Ref. S8; f Ref. S9.
a
N(% electrostr)
b
“R” indicates a value
References S1 T. G. Pedersen, C. Dethlefsen and A. Hvidt, Carlsberg Res. Commun., 1984, 49, 445–455. S2 Y. Marcus, J. Solution Chem., 2010, 39, 1031–1038. S3 CRC Press/Taylor and Francis, Boca Raton, FL, CRC Handbook of Chemistry and Physics, 90th edn, 2010. S4 F. J. Millero, Chem. Rev., 1971, 71, 147–176. S5 Y. Marcus and G. Hefter, Chem. Rev., 2004, 104, 3405–3452. S6 C. Saunderson and R. B. Ferguson, Acta Crystallogr., 1961, 14, 321–321. S7 R. Yode, in e-EROS Encyclopedia of Reagents for Organic Synthesis, John Wiley & Sons, Ltd, 2015, ch. Cesium Acetate, pp. 1–11. S8 D. A. Lee, Inorg. Chem., 1964, 3, 289–290. S9 VWR, Sodium thiocyanate Density, 2014, https://ca.vwr.com/store/catalog/product.jsp?catalog_ number=CAAA33388-A3.
S6
Standard molar volumes of electrolytes
fluoride
chloride
bromide
iodide
thiocyanate
perchlorate
Li Na K
Li Na K Rb Cs
rubidium
Li Na K Rb Cs
potassium
Li Na K Rb Cs
sodium
Li Na K Rb Cs
lithium
Li Na K Rb Cs
protic solvents caesium
50
1
mol
25
25
3
cm
cm
3
mol
1
50
0
-25
F Cl Br I ClO4
F Cl Br I ClO4
F Cl Br I SCN ClO4
F Cl Br I SCN ClO4
F Cl Br I SCN ClO4
-25
0
cation
anion
Fig. S1 Standard molar volume of alkali metal salts in methanol grouped by cation (left) and by anion (right).
sodium
potassium
rubidium
acetate
caesium
40
40
mol
1
60
20
fluoride
chloride
bromide
iodide
20
3
Cs
Rb
K
Li
Na
Cs
K
Rb
Na
Li
K
Cs
Rb
Na
Li
Cs
K
Rb
Li
Na
Cs
Li
I
AcO
Cl
Br
I
F
F
Cl
Br
I
AcO
Br
F
Cl
I
AcO
Br
F
Cl
I
AcO
Cl
-40 F
-20
-40
K
0
-20
Na
cm
0
Br
cm
3
mol
1
lithium 60
cation
anion
Fig. S2 Standard molar volume of alkali metal salts in ethanol grouped by cation (left) and by anion (right).
1
60
thiocyanate
fluoride
chloride
bromide
iodide
Li Na K Rb Cs
caesium
Li Na K Rb Cs
rubidium
Li Na K Rb Cs
potassium
Li Na K Rb Cs
sodium
perchlorate
60
mol
mol 40
cm
3
cm
3
40
20
20
0
Li Na K Rb Cs
F Cl Br I ClO4
F Cl Br I ClO4
F Cl Br I SCN ClO4
F Cl Br I SCN ClO4
F Cl Br I SCN ClO4
0 Li Na K
1
lithium
cation
anion
Fig. S3 Standard molar volume of alkali metal salts in formamide grouped by cation (left) and by anion (right).
lithium
sodium
potassium
caesium
chloride
bromide
thiocyanate
iodide
perchlorate
60 1
mol
40
40
cm
3
cm
3
mol
1
60
20
0
20
cation
Fig. S4 Standard molar volume of alkali metal salts in N-Methylformamide grouped by cation (left) and by anion (right).
S7
Cs
K
Li
Na
K
Li
Na
Cs
K
Li
Na
Cs
K
Na
Li
K
Cs
Li
anion
Na
ClO4
I
Br
Cl
ClO4
I
SCN
Br
Cl
ClO4
SCN
I
Br
Cl
ClO4
SCN
I
Cl
Br
0
lithium
sodium
potassium
rubidium
fluoride
caesium
bromide
iodide
1
mol
1
40
3
cm
20
20
K
Cs
Li
Na
Cs
Rb
K
Rb
Li
Na
Cs
K
Rb
Li
Na
Cs
K
Li
I
Br
F
Cl
Br
I
Cl
I
F
Cl
Br
I
F
Br
F
Cl
I
Br
F
Cl
Rb
0
0
Na
mol
40
3
cm
chloride
60
60
cation
anion
Fig. S5 Standard molar volume of alkali metal salts in ethylene glycol grouped by cation (left) and by anion (right).
aprotic solvents lithium
sodium
potassium
rubidium
caesium
chloride
60
perchlorate
mol
1
1
40
cm
3
40
20
0
20
anion
Cs
Rb
K
Na
Li
Cs
K
Rb
Li
Na
Cs
K
Rb
Li
Na
Cs
K
Rb
Li
I
ClO4
Cl
Br
ClO4
I
Br
Cl
ClO4
I
Br
Cl
I
ClO4
Cl
Br
I
ClO4
Cl
Br
0 Na
mol
iodide
60
3
cm
bromide
cation
Fig. S6 Standard molar volume of alkali metal salts in propylene carbonate grouped by cation (left) and by anion (right).
lithium
sodium
potassium
iodide
60
mol
1
1
cm
3
40
20
0
20
anion
K
Na
Li
K
Li
ClO4
I
ClO4
I
ClO4
I
0 Na
mol
40
3
cm
perchlorate
60
cation
caesium
60
bromide
iodide
perchlorate
mol
1
1
mol
chloride
60
40
40
cm
3
3
cm
fluoride
Li Na K Rb Cs
rubidium
Li Na K Rb Cs
potassium
Li Na K Rb Cs
sodium
Li Na K Rb Cs
lithium
Li Na K Rb Cs
Fig. S7 Standard molar volume of alkali metal salts in ethylene carbonate grouped by cation (left) and by anion (right).
20
0
20
F Cl Br I ClO4
F Cl Br I ClO4
F Cl Br I ClO4
F Cl Br I ClO4
F Cl Br I ClO4
0
cation
anion
Fig. S8 Standard molar volume of alkali metal salts in dimethyl sulfoxide grouped by cation (left) and by anion (right).
S8
sodium
chloride
1
0
bromide
iodide
perchlorate
0
mol
mol -25
cm
cm
3
3
-25
-75
anion
Na
Li
Na
Li
Na
Li
Li
Br
Cl
I
Br
Cl
I
-75 ClO4
-50
ClO4
-50
Na
1
lithium
cation
Fig. S9 Standard molar volume of alkali metal salts in acetone grouped by cation (left) and by anion (right).
lithium
sodium
potassium
rubidium
caesium
chloride
40
bromide
thiocyanate
iodide
perchlorate
1
mol
20
20
3
cm
0
-20
0
anion
Cs
K
Rb
Na
K
Li
Li
Na
Cs
K
Rb
Li
Na
Cs
K
Rb
Na
Li
Cs
Rb
K
Li
I ClO4
Br
Cl
I ClO4
Cl
Br
I
SCN ClO4
Br
Cl
I
SCN ClO4
Br
Cl
I
SCN ClO4
Cl
Br
-20 Na
cm
3
mol
1
40
cation
Fig. S10 Standard molar volume of alkali metal salts in acetonitrile grouped by cation (left) and by anion (right).
potassium
rubidium
caesium
chloride
1
sodium
mol
40
bromide
iodide
perchlorate
40
3
cm
20
0
20
anion
cation
Fig. S11 Standard molar volume of alkali metal salts in N,N-Dimethylformamide grouped by cation (left) and by anion (right).
S9
Cs
Rb
K
Na
Li
Cs
Rb
K
Na
Li
Cs
Rb
K
Li
Na
Cs
Rb
K
Li
ClO4
I
Cl
Br
ClO4
I
Br
Cl
I
ClO4
Cl
Br
I
ClO4
Br
Cl
ClO4
I
Cl
Br
0 Na
cm
3
mol
1
lithium
electrostrictive volume of electrolytes
caesium M M M M C
0
fluoride
chloride
bromide
iodide
thiocyanate
perchlorate
C M M M M
M M M M M
M M M M M
M M M M M
M C C
S C C C C
K Na Li
rubidium C M M M C
Cs Na Rb K Li
potassium M M M M M C
Na Rb K Cs Li
sodium M M M S M C
Na Rb K Cs Li
lithium M M C M M C
Rb Na Cs Li K
protic solvents
1
mol 3
-20
cm -30
-10 -20 -30
-40 I F Cl Br ClO4
F I Cl Br ClO4
I F Cl SCN Br ClO4
F Cl I ClO4 Br SCN
F Cl SCN I Br ClO4
-40 Na Rb Cs K Li
cm
3
mol
1
0
-10
cation
anion
Fig. S12 Standard molar electrostrictive volume of alkali metal salts in methanol grouped by cation (left) and by anion (right).
potassium
rubidium
caesium
M M M M M
C M M M
M M M C M
1
1
mol
fluoride
chloride
bromide
iodide
M C M M M
M M M M M
M M M M M
M M M M M
-10 -20
3
Cs
Rb
K
Li
Na
Cs
K
Rb
Na
Li
K
Cs
Rb
Na
Li
K
Cs
Na
Li
Cl
AcO
I
Br
F
Cl
I
F
Br
Cl
Br
AcO
I
F
Cl
AcO
Br
I
F
Cl
I
AcO
F
-50 Br
-40
-50
Rb
-30
-40
K
cm
-30
Na
mol cm
3
-20
C M M
0
0 -10
C
Li
sodium M M M M M
Cs
acetate
lithium M M M C M
cation
anion
iodide
thiocyanate
perchlorate
C M M M M
M M M M M
M M M M M
M M M M M
C M C
S C C C C
Cs Na Rb K Li
Li K Na
5 M M C M M C
M M M M S C
M M M M M C
C M M M C
M M M M C
mol
1
5 0
cm
3
-5 -10
-5
Cl Br I F ClO4
F Cl Br I ClO4
Cl Br F I SCN ClO4
Cl Br F I ClO4 SCN
F Br SCN Cl I ClO4
-10
Na Cs Rb Li K
1
mol
bromide
10
3
cm
chloride
caesium
rubidium
10
0
fluoride
Na Cs Rb Li K
potassium
sodium
Na Cs K Rb Li
lithium
Rb Na Li K Cs
Fig. S13 Standard molar electrostrictive volume of alkali metal salts in ethanol grouped by cation (left) and by anion (right).
cation
anion
Fig. S14 Standard molar electrostrictive volume of alkali metal salts in formamide grouped by cation (left) and by anion (right).
lithium
potassium
sodium
caesium
chloride
thiocyanate
iodide
mol
-5
M
M
M
M
M
M
M
M
M
M
M
M
C
M
C
S
C
C
C
-5
cm
3
0
K
C
Li
M
Cs
M
Na
M
Na
C
K
M
Li
M
Li
M
Na
M
K
C
Cs
S
Na
M
K
M
Cs
M
Li
C
Li
M
Na
M
K
C
perchlorate
Cs
M
1
0
bromide
5
cm
3
mol
1
5
-10
-10
-15 ClO4
Cl
Br
I
ClO4
Cl
SCN
I
Br
ClO4
SCN
Cl
I
Br
Cl
ClO4
I
Br
SCN
-15
anion
cation
Fig. S15 Standard molar electrostrictive volume of alkali metal salts in N-Methylformamide grouped by cation (left) and by anion (right).
S10
M
M
M
M
M
C
M
M
chloride
M
M
M
bromide
M
M
M
M
M
M
M
iodide
M
M
M
M
M
M
M
0 1
mol
1
-10
3
cm
-20
-20
K
Na
K
Rb
Li
Rb
Br
I
Cl
F
Cl
Br
I
F
I
Br
Cl
I
F
Cl
Br
I
F
Cl
F
Br
Na
-30
-30
Cs
mol
-10
3
cm
M
Li
C
Cs
M
fluoride
caesium
rubidium
M
Cs
M
Rb
M
M
Rb
M
K
M
Li
M
Na
M
K
potassium
sodium M
Cs
M
Li
M
Na
lithium M
0
cation
anion
Fig. S16 Standard molar electrostrictive volume of alkali metal salts in ethylene glycol grouped by cation (left) and by anion (right).
aprotic solvents
C
M
M
M
M
M
M
M
M
M
M
perchlorate
M
M
M
S
C
C
C
C
cm
3
-10
-5 -10
ClO4
Br
I
Cl
Br
ClO4
I
Cl
ClO4
I
Br
Cl
Br
I
ClO4
Cl
I
-20 ClO4
-20 Cl
-15
Br
-15
anion
Na
-5
Na
mol
1
1
mol 3
iodide
M
0
0
cm
bromide
M
K
M
Li
M
Cs
M
Rb
C
K
M
Li
M
Rb
M
chloride
caesium
rubidium
C
Cs
M
K
M
Na
M
Rb
M
Li
S
Cs
M
K
M
Rb
potassium
sodium C
Na
M
Li
M
Cs
lithium M
cation
Fig. S17 Standard molar electrostrictive volume of alkali metal salts in propylene carbonate grouped by cation (left) and by anion (right).
lithium
iodide
potassium
sodium
C
cm
-4
-8
0
M
M
M
Na
M
Li
M
K
S
mol
C
3
M
1
1
S
C
C
-4
anion
K
Li
ClO4
I
I
ClO4
ClO4
I
-8
Na
mol 3
cm
0
perchlorate
4
4
cation
M M M M
S
M M M M C
C M M M C
M M M M C
mol
1
0
3
-5
cm
-10
bromide
iodide
perchlorate
C M M M M
M M M M M
M M M M M
M M M M M
S
-5 -10
Cl Br F I ClO4
-20 F Cl Br I ClO4
-20 Cl Br F I ClO4
-15
Cl F Br I ClO4
C C C C
0
-15
Cl Br F I ClO4
mol
1
M M M M C
3
chloride
5
5
cm
fluoride
Na Cs Li Rb K
caesium
Cs K Li Na Rb
rubidium
Li Na K Rb Cs
potassium
sodium
Li K Na Cs Rb
lithium
Rb Li Na K Cs
Fig. S18 Standard molar electrostrictive volume of alkali metal salts in ethylene carbonate grouped by cation (left) and by anion (right).
cation
anion
Fig. S19 Standard molar electrostrictive volume of alkali metal salts in dimethyl sulfoxide grouped by cation (left) and by anion (right).
S11
chloride
M
S
M
M
M
M
M
iodide M
perchlorate M
C
S
0
-100
-100 Br
I
Cl
Br
I
Cl
ClO4
-75
ClO4
-75
anion
Na
-50
Li
cm
-50
-25
Na
3
-25
Li
mol
1
1
mol 3
cm
bromide
M
Na
M
Li
sodium M
Na
C
Li
lithium M
0
cation
Fig. S20 Standard molar electrostrictive volume of alkali metal salts in acetone grouped by cation (left) and by anion (right).
M
M
C
M
M
M
chloride
bromide
thiocyanate
iodide
C M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
C
C
Na
M
Li
caesium
rubidium C
K
M
Cs
M
Rb
M
Na
M
Li
C
K
S
Na
M
Cs
M
Li
M
Rb
C
K
potassium
sodium
M
Na
C
Cs
M
Rb
lithium M
0
perchlorate S
C
C
C
C
1
-10
mol
-20
-20
cm
3
3
-30 -40
-30 -40
anion
K
Li
Cs
Rb
Na
-50
I ClO4
Br
Cl
I ClO4
Cl
Br
I ClO4
Br
SCN
Cl
SCN
Br
I ClO4
Cl
I ClO4
SCN
Cl
Br
-50
K
cm
-10
Li
mol
1
0
cation
Fig. S21 Standard molar electrostrictive volume of alkali metal salts in acetonitrile grouped by cation (left) and by anion (right).
M
M
M
M
M
M
M
iodide M
perchlorate
M
M
M
M
M
S
C
C
C
C
mol
1
1
-10
-10
cm
3
3
-20
-30
-20
ClO4
I
Cl
Br
ClO4
I
Cl
Br
I
ClO4
Cl
Br
ClO4
I
Br
Cl
ClO4
I
Cl
Br
-30
anion
Na
mol
M
0
0
cm
bromide
M
K
C
Li
M
Cs
M
Rb
M
Na
C
Li
M
Na
M
chloride
caesium
rubidium M
K
C
Cs
M
Rb
M
Cs
M
K
S
Li
M
Rb
M
Li
M
Na
potassium
sodium C
Cs
M
K
M
Rb
lithium M
cation
Fig. S22 Standard molar electrostrictive volume of alkali metal salts in N,N-Dimethylformamide grouped by cation (left) and by anion (right).
S12
normalised electrostrictive volume of electrolytes
rubidium
caesium
C M M M C
C M M M M
0
N%
-100
fluoride
chloride
bromide
iodide
thiocyanate
perchlorate
M C M M M
M M M M M
M M M M M
M M M M M
M C C
C C C C S
K + Li + Na
potassium C M M M M M
Cs + Rb + K + Li + Na
sodium S C M M M M
Cs + Rb + K + Li + Na
lithium C C M M M M
Cs + Rb + K + Na + Li
0
-100
-200
+
Cs + K + Rb + Li + Na
+
+
+
+
-
ClO4 I Br Cl F
-
ClO4 I Br Cl F
-
ClO4 SCN I Br Cl F
-
ClO4 SCN I Br Cl F
-
ClO4 SCN I Br Cl F
-200
+
N%
Cs + Rb + K + Na + Li
protic solvents
cation
anion
Fig. S23 Normalised standard molar electrostrictive volume of alkali metal salts in methanol grouped by cation (left) and by anion (right).
lithium
sodium
potassium
rubidium
caesium
C M M M M
M M M M M
M M M M M
M M M C
C M M M M
0
N%
chloride
bromide
iodide
M M M M M
M M M M M
M M M M M
+
+
Li
Na
+
+
K
+
Cs
Rb
+
+
Li
+
Na
+
K
Cs
Rb
+
+
+
Li
+
K
Na
Rb
Cs
+
+
+
+
Li
+
K
Na
+
+
Rb
+
Cs
+
Li
Na
+
+
K
Cs
-
fluoride M C M M M
-
F
Cl
-
-
Br
-
I
AcO
-
F
Cl
-
-
-
I
Br
-
-
F
Cl
Br
-
-
-
I
AcO
-
-
F
-
Cl
Br
-
I
AcO
F
Cl
Br
-
-400 -
-400 -
-300
-
-200
-300
-
-200
-
-100
AcO
acetate C M M C
0
-100
I
N%
cation
anion
C M M M M M
C M M M C
bromide
iodide
thiocyanate
perchlorate
M M C M M
M M M M M
M M M M M
M M M M M
C M C
C C C C S
K + Li + Rb + Cs + Na
C S M M M M
chloride
caesium
10 C M C M M M
fluoride
Na + K + Li
rubidium
Li + K + Rb + Cs + Na
potassium
Cs + Rb + K + Li + Na
sodium
Cs + Rb + K + Li + Na
lithium
C M M M M
N%
0
10 0
-10
-10
-20
-20
-30
-30
-40
-40
+
+
+
+
-50 +
-
ClO4 I F Br Cl
I Br Cl F
ClO4 -
SCN I Br F Cl
ClO4 -
-
SCN ClO4 I Br Cl F
-
ClO4 I SCN Cl Br F
-50
+
N%
Cs + K + Rb + Na + Li
Fig. S24 Normalised standard molar electrostrictive volume of alkali metal salts in ethanol grouped by cation (left) and by anion (right).
cation
anion
Fig. S25 Normalised standard molar electrostrictive volume of alkali metal salts in formamide grouped by cation (left) and by anion (right).
S13
thiocyanate
iodide
M
M
M
M
M
M
M
M
M
M
M
C
M
C
+
-10
M
+
N%
perchlorate C
C
C
S
+
bromide
M
+
chloride
M
+
M
C
+
M
+
caesium
M
+
M
+
M
+
C
+
M
+
potassium
M
+
M
S
+
C
M
+
sodium
M
+
C
+
M
C
0
+
lithium
0 -10
-20
-20
-30
-30
Na
Li
+
K
Cs
Li
K
Na
Li
Cs
K
anion
Na
Li
Na
K
Cs
Li
Cs
Na
-
-
-40
Br
-
I
Cl
-
ClO4
-
Br
-
-
I
Cl
-
-
ClO4
SCN
-
-
Br
Cl
-
-
I
-
ClO4
SCN
-
-
Cl
Br
-
-
SCN
I
-
ClO4
-40
K
N%
cation
Fig. S26 Normalised standard molar electrostrictive volume of alkali metal salts in N-Methylformamide grouped by cation (left) and by anion (right).
M
M
M
M
M
M
M
M
M
M
+
+
+
+
M
M
M
M
+
M
+
M
+
M
+
iodide
M
Rb
Na
K
Li
Cs
Li
Na
K
Rb
Cs
-
F
Cl
-
-
I
-
Br
-
I
-
F
-
Cl
-
Br
-
F
-
Cl
-
I
Br
-
-
F
-
Cl
-
-
I
Br
-
F
Cl
-
-100
-
-100
-
-50
I
bromide
C
0
-50
Br
chloride
M
+
N%
Cs
M
+
M
Li
M
+
M
+
fluoride
caesium M
Na
C
+
M
K
rubidium M
+
M
Cs
M
Rb
M
+
M
+
potassium M
Li
M
Na
M
+
M
+
sodium M
K
M
+
M
+
M
0
Rb
lithium
N%
cation
anion
Fig. S27 Normalised standard molar electrostrictive volume of alkali metal salts in ethylene glycol grouped by cation (left) and by anion (right).
aprotic solvents
M
M
M
perchlorate
M
M
M
C
C
C
C
S
+
M
+
M
+
M
+
M
+
M
+
M
+
M
+
iodide
M
Na
Li
Cs
Rb
K
Li
+
Na
K
Cs
anion
Rb
-
Cl
-
-
I
Br
-
ClO4
-
Cl
I
-
-
Br
-
ClO4
-
Cl
-
I
-
Br
-
ClO4
-
Cl
Br
I
-
Cl
Br
I
-
-
-60
-
-60
ClO4
-40
-
-40
-
-20
-
-20
ClO4
bromide
M
0
Cs
N%
+
chloride M
+
M
Li
M
Na
C
+
caesium M
+
M
K
M
+
C
Rb
rubidium
M
+
M
Cs
M
+
C
Li
potassium M
+
M
Na
M
+
S
K
sodium M
+
M
M
+
C
0
Rb
lithium
N%
cation
Fig. S28 Normalised standard molar electrostrictive volume of alkali metal salts in propylene carbonate grouped by cation (left) and by anion (right).
C
S
C
+
M
+
Na
Li
-
I
-
-
I
I
-
ClO4
-10
ClO4
-10
-
-5
ClO4
M
0
-5
anion
perchlorate
M
Na
0
N%
+
iodide M
K
C
+
potassium M
K
S
+
sodium M
Li
C
+
lithium
N%
cation
Fig. S29 Normalised standard molar electrostrictive volume of alkali metal salts in ethylene carbonate grouped by cation (left) and by anion (right).
S14
-150
bromide
iodide
M M M M M
M M M M M
+
-
-
I Br Cl F
-
-
I Br Cl F
-
-
I Br Cl F
-
-
I Br Cl F
-
-
I Br Cl F
chloride M M M M M
perchlorate C C C C
S
+
-150 ClO4
-100
ClO4
-100
ClO4
-50
ClO4
-50
ClO4
fluoride M C M M M
0
K + Cs + Rb + Li + Na
N%
+
caesium C M M M M
Rb + Cs + K + Na + Li
rubidium C M M M C
+
potassium C M M M M
Cs + Rb + K + Na + Li
M M M M
+
S
Cs + Rb + K + Na + Li
sodium
C M M M M
0
Cs + Rb + K + Na + Li
lithium
N%
cation
anion
Fig. S30 Normalised standard molar electrostrictive volume of alkali metal salts in dimethyl sulfoxide grouped by cation (left) and by anion (right).
perchlorate M
S
C
+
Li
Na
anion
+
-
Cl
Br
-
-
I
Cl
-
iodide M
Na
-400 Br
M
+
-400 -
M
Li
-300
ClO4
-300
-
-200
-
-200
ClO4
-100
-
M
0
-100
I
bromide
M
+
N%
M
Na
S
+
chloride
M
Li
M
+
M
Na
M
+
sodium
C
Li
M
0
+
lithium
N%
cation
Fig. S31 Normalised standard molar electrostrictive volume of alkali metal salts in acetone grouped by cation (left) and by anion (right).
caesium
M M M
thiocyanate
chloride
bromide
iodide
M M M M M
M M M M M
M M M M M
M M M
C
N%
-50
M
C
C
perchlorate C
C
C
C
S
+
C
+
rubidium
M M M M
C
+
potassium
M M M
+
C
+
S
+
sodium
M M M
+
C
C
0
+
lithium
0
-50
-100
-100
-150
anion
Li
Na
Rb
K
Cs
Li
Na
K
+
+
Na
+
Li
+
K
Rb
+
Cs
+
Li
+
+
K
Na
Rb
Cs
+
+
+
+
Li
+
K
Na
+
Cs
+
-
Cl
Br
-
I
-
-
ClO4
-
-
Cl
Br
-
I
-
ClO4
-
-
Cl
Br
I
-
-
SCN
-
ClO4
-
-
Cl
I
Br
-
SCN
ClO4 -
-
-
Cl
Br
-
I
-
-
SCN
ClO4
-150
Rb
N%
cation
Fig. S32 Normalised standard molar electrostrictive volume of alkali metal salts in acetonitrile grouped by cation (left) and by anion (right).
M
M
M
M
M
M
M
M
M
M
M
M
C
C
C
S
C
+
+
+
+
+
+
+
+
perchlorate
M
+
iodide
M
Li
Na
Cs
Rb
K
Li
Na
K
Rb
-
Cl
Br
-
-
I
-
ClO4
-
Cl
-
Br
-
I
ClO4
-
-
Cl
I
Br
-
-
ClO4
-
Cl
-
Br
I
-
-
Cl
Br
I
-
-120
ClO4
-120 -
-80
-
-80
-
-40
ClO4
-40
anion
bromide
M
0
Cs
N%
+
chloride M
Li
M
+
M
Na
C
+
caesium M
+
M
K
M
+
rubidium C
Cs
M
Rb
M
+
M
+
C
Li
potassium M
Na
M
+
M
+
S
K
sodium M
+
M
+
M
Cs
C
0
Rb
lithium
N%
cation
Fig. S33 Normalised standard molar electrostrictive volume of alkali metal salts in N,N-Dimethylformamide grouped by cation (left) and by anion (right).
S15
