__Significant results __**(1979 - 201 3 ) (Raji Heyrovska, Ph.
D.)
(See list of publications in
http://www.jh-inst.cas.cz/~rheyrovs, for work before 1979)**

Contents:

I. Partial dissociation and hydration of Strong electrolytes at all concentrations found to be correct (Arrhenius, Van't Hoff and Ostwald were right; see publications:1979-).

II. Distances of closest approach of ions (have been evaluated using degrees of dissociation in Bjerrum's equation; see publications: 1999).

III. "Anomalous" Stokes ionic radii explained (so-called "anomaly" disappears on using "local" instead of "bulk' viscosity in the Stokes-Einstein Eqn.; see publication: 1989).

IV. "Wet-and-measure" polarography (uses small amounts of solution held by surface tension between a silver ring and the glass capillary with Hg-drop; see publication: 1992).

V. Current spike polarography for films and surfaces (tip of the mercury drop from the glass capillary contacts the solution at the end of its drop life; see publication: 1993).

VI. Rest mass based neutron numbers, N(rm) (Use of rest masses shows
that for atomic masses A > 108, N(rm) = N -1 and for A > 254, **N(rm) = N -
2**; see publications: 1992,
1998, 2010).

VII. Interpretation of Michelson & Morley's observations (using Galilean kinematics, without invoking the contraction of distance and dilation of time hypotheses demanded by the special theory of relativity) (First author: Albert Heyrovsky; see publication: 1994).

VIII. Mass defect due to neutrinos evaluated from nuclear mass defects (based on the fact that fusion of a proton and a neutron to form a deuteron releases a neutrino, antineutrino pair and causes a definite mass defect attributable to neutrinos. A simple equation is provided; see publications: 1998, 2010).

IX. A new theory of the energy of the hydrogen atom (shows that the Bohr radius is divided into two Golden sections pertaining to the electron and proton and that the differenec in the two terms in the Rydberg equation in spectrocopy arises due to the electrostatic energy in the ground state. This further leads to the assignment of Golden ratio based ionic radii which explain quantitatively the interionic distances in all alkali halides and also to the additivity of atomic/ionic radii in bond lengths in general; see publications: 1999 - 2011).

X. The absolute potentials of the standard hydrogen electrode and hence of redox couples of elements of the Periodic Table have been obtained, (unambigously by a new linear correlation of the gaseous ionization potentials with standard aquoeus redox potentials; see publications: 2009-).

XI. Other significant results (- 2013)

XII. Women in Science (2002 - 2011)

------------------------------------------------------------------------------------------------------------------------------

`I.
Partial
dissociation of Strong electrolytes (Arrhenius, Van't
Hoff and Ostwald were right!)`` `

`Introduction:
I got acquainted with the properties of strong electrolytes
when I was working for my Ph. D. degree. Ever since, I was
wondering why the theory of electrolytes was so complicated.
It was based on extensions to higher concentrations of the
Debye-Huckel (1923) equations, which were valid only for
very dilute solutions, and there was no unified
interpretation of the thermodynamic properties over the
whole concentration range (e.g., see: R. A. Robinson and R.
H. Stokes, Electrolyte Solutions, Butterworths, `London
1955, 1970).

`During the years
1979 - 1984, by a systematic analysis of the existing data
on the thermodynamic properties of electrolytes, it became
gradually clear to me that the assumption of complete
dissociation of strong electrolytes that prevailed from 1923
onwards had to be abandoned in favor of the earlier van't
Hoff's factor for non-ideality and its interpretation by
Arrhenius through the idea of partial dissociation. On
combining the ideas of partial dissociation and hydration
(as Arrhenius himself had suggested) as pointed out by
Bousefield (1917), I could show unambiguously
in 1984, that the thermodynamic properties of electrolytes
could be quantitatively explained using simple equations ``(a century after Arrhenius wrote his
dissertation for the Ph. D. in 1884!)``. `

`Subsequently, in
1987 I could explain the solution properties quantitatively
from zero upto a higher concentration of about 3.5m by using
``the degrees of dissociation
and hydration numbers obtained from ``the data on vapor pressure of solutions. It
was published in a detailed form in: R. Heyrovska, Chapter
6, "Electrochemistry,
Past and Present" (ACS Symposium Series 390, Editors: J.T.
Stock and M.V. Orna, ACS, Washington DC, 1989). In 1995, on
realizing that the bulk (for osmotic properties) and surface (for
vapour pressure and other interfacial properties)
hydration numbers were different, I could
re-evaluate the degrees of dissociation from
osmotic coefficients and quantitatively explain the thermodynamic
properties (like the EMF of concentrtaion cells
and molal volumes of solutions) of a typical strong
electrolyte like NaCl(aq) from "zero to saturation" for the first time.
`

`A full paper on
this was accepted with encouraging remarks in: R. Heyrovska, Journal of Electrochemical Society,
143 (1996) 1789. Thus, since solution properties
could now be explained quantitatively using concentrations
and volumes of ions and ion pairs and of free water, the arbitrary
thermodynamic correction factors,`` evaluated
on the assumption of complete dissociation of
electrolytes,`` like
"activity and osmotic coefficients" are unnecessary. `

`Since 1996, I
have extended the above work to all the alkali
halides, strong acids, bases and many more strong
electrolytes. After my talk on the subject at
Harvard University, (my host) Prof. J.N. Butler, ``invited me
to write a short account in his book, (R. Heyrovska in: ``"Ionic
Equilibrium", Ed. J.N. Butler, (John Wiley and Sons, New
York, 1998), chapter 11, `pp. 477- 481)`,`` which he
had almost completed. ``An invited full review of my work is in: R. Heyrovska, Chemicke
Listy, 92 (1998) 157 (in
English). Several Tables of data on the degrees of
dissociation of many electrolytes are now in my webpage at http://www.jh-inst.cas.cz/~rheyrovs,
in R. Heyrovska,
Croatica Chemica Acta, 70 (1997) 39 (all alklai
halides) and in R.
Heyrovska, `

`In 2003, it was a
great honour for me to have been awarded the Invited
Plenary Lecturership in the "Svante Arrhenius Symposium"
commemorating the award of the Nobel Prize to him in 1903.
The
text of this Lecture is in my above webpage (http://www.jh-inst.cas.cz/~rheyrovs/text-sa-.htm)
and has now been published along with more data in: R. Heyrovska,
Electroanalysis, 18 (2006) 351-361.`

`Further, I have
worked out a concise
equation of state for solutions of electrolytes, based on
hydration and partial dissociation, which incorporates the
thermodynamic laws (see: R. Heyrovska, Special
Issue of ENTROPY, 6 (2004) 128). This was on the
analogous lines of an equation of state that I had developed
earlier for gases (presented at a conference on the Second
Law of Thermodynamics in San Diego, CA, in 2002) in: R. Heyrovska, AIP
Conference Proceedings, 643 (2002) 157. `

`Outline/summary
of the work: The idea of partial dissociation of
strong electrolytes in aqueous solutions due to Arrhenius
was highly appreciated at a time when solution chemistry was
in bad need of it. ``The use of the conductivity ratio for the
degree of dissociation ``could satisfactorily explain many experimental
results for dilute solutions. However, since the
conductivity ratio became unsatisfactory for higher
concentrations, especially for highly dissociated
electrolytes like NaCl, Lewis and Randall arbitrarily
introduced the "activity coefficients" as empirical
non-ideality correction factors for concentrations (in the
absence of an exact knowledge of the concentration of the
undissociated form). Since the Debye-Huckel theory, which
treated non-ideality as due to interionic interactions, was
able to account for the dependence of the actvity
coefficient (and other properties of electrolyte solutions)
on the square root of concentration for dilute solutions, strong electrolytes were
"assumed" (erroneously)
to be completely dissociated as shown, `

`NaCl
-----> Na ^{+} + Cl^{-} ... (1) `

`The DH equations
were then gradually extended by the addition of more and
more parameters for explaining the solution properties over
larger ranges of concentration (and finally upto saturation,
e.g., see the Pitzer equations in: D. G. Archer, J. Phys.
Chem. Ref. Data 28 (1999) 1 and elsewhere).
`

`As these elaborate
parametrical equations, based on the idea of complete
dissociation, could not provide a molecular insight into
non-ideality, ``the author undertook a systematic
re-investigation of the available thermodynamic data as
such. Eventually, by evaluating the degrees of dissociation
from vapor pressure or solvent activity data, it was found
that strong electrolytes are
indeed only partially dissociated in aqueous solutions as
originally supposed by Arrhenius a century earlier:
`

`NaCl
<=====> Na ^{+} + Cl^{-} ... (2) `

`(1-
`a`) <=====> `a` + `a`; sum = i
= (1+`a`)`

`Thus, a fr`a`ction `a` of one mole of NaCl dissociates into `a` moles each of Na ^{+} and Cl^{-}
ions, amounting to 2`a

`With the degrees
of dissociation and hydration numbers (both surface and
bulk) obtained from the experimental values of solvent
activities (a _{A}), many thermodynamic properties
could be interpreted quantitatively using simple
mathematical relations, valid from zero even up to
saturation in many cases. The DH equations were shown to be
asymptotic laws for complete dissociation at infinite
dilution. Hydration
and ionic association/dissociation thus proved to be the
causes of non-ideality of solution properties at all
concentrtaions. `

`"The thermodynamic
dissociation constant", K for NaCl(aq) was
shown to obey the Guldberg and Waage's Law, defined as, `

`K = (
c _{i})^{2} /c_{ip} =
constant (at all
concentrations)`

`where c _{i}
= `a

`Therefore, since
now we have the exact values
of the thermodynamic "ionic molality, `a`m" of an ion at any
molality m of the electrolyte, there is "no need for the
activity and osmotic coefficients", which are
evaluated based on the idea of complete electrolytic
dissociation".
`

R. Heyrovska, Chemicke Listy, 92 (1998) 157.

http://www.jh-inst.cas.cz/~rheyrovs/text-sa-.htm

`II. Distances
of closest approach of ions
(evaluated using degrees od dissociation in Bjerrum's
equation)`` `

`Bjerrum thought
that in a strong electrolyte like NaCl in aqueous solutions,
ion pairs are unlikely since the critical distance of
approach for ion pair formation, q ~ 3.7 `

`(1-`a`)/c =
2.755 Q(b); Q(b) = f(a) `

`where Q(b), the
Bjerrum's integral is a function of "a". For
NaCl(aq), ``(1/a)
changes linearly with 1/m and ``even at saturation, a < q``, the
critical distance.
References: R. Heyrovska: Journal of Molecular Liquids, 81
(1999) 83 (Letter)
and Current Science, 76 (1999)
179 (full paper).
`

`III. "Anomalous"
Stokes ionic radii explained (so-called`
"anomaly" disappears on using "local" instead of "bulk"
viscosity in the S-E Eqn)` `

`The Stokes ionic radius, R _{Si} is
obtained from the Stokes-Einstein
equation (S-E eqn), `

`D _{iw}^{o} =
kT/6`ph

`where `h^{o}` is the coefficient of viscosity of the pure
solvent (water, w) in the bulk. The "anomalous" values of R _{Si}
are usually associated with ionic hydration. It is shown
here that the "anomaly" is actually due to the
(incorrect) use of the coefficient of viscosity of the
bulk water, `h

`D _{iw}^{o}
= kT/6`ph

`where
R _{Si} = R_{wi} `h

`Reference:
R. Heyrovska,
Chemical Physics Letters, 163 (1989) 207. `

`IV. "Wet-and-measure"
polarography (uses
small amounts of solution sticking by surface tension
between a silver ring and the glass capillary)`` `

`This new device shows that the tiny volume
of solution that sticks by surface tension betwen a silver
ring and the end of the glass capillary of the mercury ``electrode is quite enough for polarogarphy,
since it gives the same polarograms as those with mercury
electrodes (both DME and HME) dipping in bigger volumes of
solution as in conventional polarography.
Reference:
R. Heyrovska,
Journal of Electrochemical Society, 139 (1992) L50. `

`V. Current
spike polarography for films and surfaces
(tip of the mercury drop contacts the solution at the end
its of drop life)`` `

`This is another
new technique: the mercury drop contacts the surface or film
of the solution in a silver ring electrode at the end of its
drop life and hence a current spike is obtained and
recorded. This is sensitive to oxygen and can be used as an
oxygen sensor, also for measuring the difference between
the surface and bulk potentials (`c` -potential), for fast electron transfer
processes and for
detecting the polarographic maxima of the 1st and
2nd kinds.
Reference: R.
Heyrovska,
Langmuir, 9 (1993)
1962.
`

`VI. "Rest mass based
neutron numbers, N(rm)"`` (exact rest masses show that
for A > 108, N(r,m) = N - 1 and for A > 254, ``N(r,m) = N - 2``)`

`These values of ``N(rm) ``are based
on
the exact rest masses of the electron (m _{e }=
0.00054858 u), proton (m_{p }= 1.0072765 u) and
neutron (m_{n} = 1.0086649 u). Note that the conventionally
used neutron numbers (N) are based on m_{e
}= 0, m_{p }= m_{n }= 1 u `

`N(rm)
= [A - Z (m _{e}+ m_{p})]/m_{n} ~ N only for atomic
masses A < 108, `

References: R. Heyrovska: Journal of Chemical Education, 69 (1992) 742; 216th Meeting of the American Chemical Society, Boston, Aug. 1998, short abstract no. 11;

`VII. Interpretation of
Michelson & Morley's observations ("without
invoking the contraction of distance hypothesis
demanded by the special theory of relativity") (First author: A.
Heyrovsky)`` `

`As the
interpretations usually involve the "contraction
of distance" and "dilation of time" hypotheses (as per the
special theory of relativity), which have NOT been directly experimentally
verified, M&M's observations are explained
here by a vector addition of the velocity of the Earth
with that of light assuming Galilean kinematics, WITHOUT the
contraction or dilation hypotheses.
Reference: A.
Heyrovsky and R. Heyrovska, Physics Essays, 7 (1994) 265.
`

`VIII. "Mass defect due to
neutrinos" evaluated from nuclear mass defects`` (based on the fact that fusion
of a proton and a neutron to form a deuteron releases a
neutrino, antineutrino pair and causes a definite mass
defect attributable to neutrinos)`

`The idea behind
this is that a neutrino, antineutrino pair is released
during the synthesis of a deuteron from a neutron and a
proton. Therefore, if the neutrinos have mass, the nuclear
mass defect, MD = (Zm _{H}+Nm_{n}) - A, where
A is the atomic mass of the nuclide X(Z.N) must also contain
the mass defect due to neutrinos. Based on this, it is
shown here that the mass defect due to neutrinos, MD(`n

`MD(`n`)/MD =
[Z/(Zm _{H}+Nm_{n})](m_{n}-m_{p})^{2}/m_{n}
`

`The values of the
" mass defect per nucleon due to neutrinos/antineutrinos",
MDPN(`n

`References: R. Heyrovska, 216th
Meeting of the American Chemical Society, Boston, Aug. 1998, short abstract
no. 9; in book form: Arjun Consultancy & Publishing
Inc., Desktop publisher, Wayne, NJ (USA), 1998, (full paper) and
in: ` http://precedings.nature.com/documents/4547/version/1
(2010)

IX. A new theory of the energy of the hydrogen atom (shows that the Bohr radius is divided into two Golden sections pertaining to the electron and proton. This leads to the assignment of Golden ratio based ionic radii which explain quantitatively the interionic distances in all alkali halides and further, to the additivity of atomic/ionic radii in bond lengths.

References: R. Heyrovska, Molecular Physics, 103 (2005) 877 - 882; Chapter 12 in: "Innovations in Chemical Biology", Editor: Bilge Sener, Springer.com, January 2009; http://precedings.nature.com/documents/3292/version/1 (2009)

**X. **Absolute
potentials of the hydrogen electrode (established
for the first time), of aqueous redox couples and of
standard reference electrodes (2009-)

**The absolute
potential of the standard hydrogen electrode (which
was so far taken arbitrarily as zero) and of redox couples of elements
of the Periodic Table have been established unambiguously from a new
simple linear correlation of aqueous standard potentials
with gaseous ionization potentials.
**

References: R. Heyrovska,
Electrochemical and Solid -State Letters, 12 (2009) F29-F30; Electrochem. Soc. Trans., 25, (2010) 159-163; Electroanalysis,
22 (2010) 903,

http://precedings.nature.com/documents/4354/version/1
(2010), see also refs 136 -140, 145.

XI. Other significant
results
(1999 - 2011) (Selected few only. Reference numbers are
as in the List of publications.)

**85.
**`Degrees
of dissociation and hydration numbers of monovalent sulphates
including ammonium sulfate (1999).
See: `http://www.electrochem.org/dl/ma/196/pdfs/2041.PDF
and a Table

**86,
96.**` Thermodynamic
significance of transfer
coefficients and E. M. F. of concentration cells (2000, 2002).
Shows that the transfer coefficient is not merely a kinetic
parameter, but is basically a thermodynamic parameter which
influences the kinetics.`

Linear relations have been shown for elements in many groups in the Periodic Table. See

92.

Using the linear relation shown above in Ref.

98.

The new concise equation of state (with association/dissociation of molecules) incorporates also heat capacities, the thermodynamic laws and entropy. The fundamentals of the 2nd law are discussed:

**102.**` A`` concise equation of
state for aqueous solutions of electrolytes
incorporating thermodynamic laws and entropy (2004).
The
new concise equation of state (with ion association and
hydration), analogous to that for gases in Ref. 98, incorportaes also
heat capacities, the thermodynamic laws and entropy:`R. Heyrovska,

**106
-110.**` Hydrogen as an atomic
condenser (2004,
2005).
While working on the ionization potentials, the
author arrived at the conclusion that the ground state Bohr
radius is divided into two Golden sections at the point of
electrical neutrality. The ionizational potential is the
difference of two terms pertaining to the proton and
electron. This
explains why the two oppositely charged particles do not
fall into each other, and shows that the two terms in the Rydberg
equation for spectra arise in the ground state term itself.
The energy of hydrogen can thus be considered as the
electromagnetic energy of the simplest atomic
condenser with the Golden mean capacity. References: `R. Heyrovska,

**110.**` The Golden ratio (`f`), ionic and atomic radii and
bond lengths (2005).
Shows that since the Bohr radius has two Golden sections,
interatomic distances (between like atoms) are divided into
two Golden sections, representing meaningful anionic and
cationic radii. The latter account for the full (as in
alkali halides) and partial ionic (like hydrogen halides)
character of some chemical bonds, and show that bond
lengths, in general, are sums of atomic/ionic radii. Tables
of ionic and atomic radii and bond lengths are provided.
Reference: `R. Heyrovska, Special Issue of Molecular Physics,
103 (2005) 877 - 882.
For more publications: see full List of publications.

Shows that the ratio of the difference in g-factors (of the electron and proton) to their sum, is equal to

Reference:

**115.**` Dependence of ion-water
distances on covalent radii, ionic radii in water and
distances of oxygen and hydrogen of water from ion/water
boundaries
(2006).
The linear dependences give the aqueous ionic radii of many
different elements and lengths of the hydration bonds, which
are all functions of the Golden ratio. The hydrogen bond
with all the halide ions is found to be have a constant
length and is the sum of the `f

Reference:

120, 123, 131. Unification of all radii by their linear dependence on Bohr radii

`Reference: `R. Heyrovska, __http://arxiv.org/ftp/arxiv/papers/0708/0708.1108.pdf
; __Philippine Journal of
Science, 137 (2): 133-139, December 2008.

**121, 122, 124 - 128**, 130, 132 - 135, 141, 142, 144, 148, 150, 151,
152, 155: (2005 - 2011): Additivity of atomic/ionic
radii in the bond lengths of many inorganic, organic, 2D
nano-materials and biochemical molecules including in DNA.

149. Balmer and Rydberg equations for
hydrogen spectra revisited: Bohr's ad hoc quantization of angular momentum was
not necessary

http://arxiv.org/ftp/arxiv/papers/1105/1105.4366.pdf
(2011)

**160. Atomic
and Ionic Radii of Elements**

International Journal of Sciences (ISSN 2305-3925) Volume 2, 82-92, Issue Mar 2013, Research Article.

**162.****
****Bond Lengths, Bond Angles and
Bohr Radii from Ionization Potentials Related via the
Golden Ratio for H**_{2}^{+}**,
O**_{2}**, O**_{3}**,
H**_{2}**O, SO**_{2}**,
NO**_{2 }**and CO**_{2}

International
Journal of Sciences (ISSN 2305-3925) Volume 2, 1-4,
Issue Apr- 2013, Research Article.

163.

R. Heyrovska,

XII. Women in Science (see full
articles in List of Publications)

References 1 - 15 (in pink): Publications (2002 - 2011) on suggestions for improving the
academic status/situation of Women in Science.

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