# Johannes Diderik van der Waals

Last updated

Johannes van der Waals
Born23 November 1837
Leiden, Netherlands
Died 8 March 1923 (aged 85)
Amsterdam, Netherlands
Nationality Dutch
Alma mater University of Leiden
Known for Laying the foundations for modern molecular physics (molecular theory)
Originating modern theory of intermolecular forces
Law of corresponding states
Real gas law
van der Waals forces
van der Waals equation of state
van der Waals radius
van der Waals surface
van der Waals molecule
Awards Nobel Prize for Physics (1910)
Scientific career
Fields Theoretical physics, thermodynamics
Institutions University of Amsterdam
Doctoral advisor Pieter Rijke
Doctoral students Diederik Korteweg
Willem Hendrik Keesom
Influences Rudolf Clausius
Ludwig Boltzmann
Josiah Willard Gibbs
Thomas Andrews
Influenced Heike Kamerlingh Onnes
Willem Hendrik Keesom
Peter Debye
Zygmunt Florenty Wróblewski
James Dewar
Fritz London
Modern molecular science (including molecular physics and molecular dynamics)
Cryogenics

Johannes Diderik van der Waals (Dutch pronunciation: (); [1] 23 November 1837 – 8 March 1923) was a Dutch theoretical physicist and thermodynamicist famous for his work on an equation of state for gases and liquids.

Theoretical physics is a branch of physics that employs mathematical models and abstractions of physical objects and systems to rationalize, explain and predict natural phenomena. This is in contrast to experimental physics, which uses experimental tools to probe these phenomena.

In thermodynamics, a thermodynamicist is someone who studies thermodynamic processes and phenomena, i.e. the physics that deal with mechanical action and relations of heat.

In physics and thermodynamics, an equation of state is a thermodynamic equation relating state variables which describe the state of matter under a given set of physical conditions, such as pressure, volume, temperature (PVT), or internal energy. Equations of state are useful in describing the properties of fluids, mixtures of fluids, solids, and the interior of stars.

## Contents

His name is primarily associated with the van der Waals equation of state that describes the behavior of gases and their condensation to the liquid phase. His name is also associated with van der Waals forces (forces between stable molecules), [2] with van der Waals molecules (small molecular clusters bound by van der Waals forces), and with van der Waals radii (sizes of molecules). As James Clerk Maxwell said about Van der Waals, "there can be no doubt that the name of Van der Waals will soon be among the foremost in molecular science." [3]

The van der Waals equation is an equation of state that generalizes the ideal gas law based on plausible reasons that real gases do not act ideally. The ideal gas law treats gas molecules as point particles that interact with their containers but not each other, meaning they neither take up space nor change kinetic energy during collisions. The ideal gas law states that volume (V) occupied by n moles of any gas has a pressure (P) at temperature (T) in kelvins given by the following relationship, where R is the gas constant:

In the physical sciences, a phase is a region of space, throughout which all physical properties of a material are essentially uniform. Examples of physical properties include density, index of refraction, magnetization and chemical composition. A simple description is that a phase is a region of material that is chemically uniform, physically distinct, and (often) mechanically separable. In a system consisting of ice and water in a glass jar, the ice cubes are one phase, the water is a second phase, and the humid air is a third phase over the ice and water. The glass of the jar is another separate phase.

A van der Waals molecule is a weakly bound complex of atoms or molecules held together by intermolecular attractions such as van der Waals forces or by hydrogen bonds. The name originated in the beginning of the 1970s when stable molecular clusters were regularly observed in molecular beam microwave spectroscopy.

In his 1873 thesis, van der Waals noted the non-ideality of real gases and attributed it to the existence of intermolecular interactions. He introduced the first equation of state derived by the assumption of a finite volume occupied by the constituent molecules. [4] Spearheaded by Ernst Mach and Wilhelm Ostwald, a strong philosophical current that denied the existence of molecules arose towards the end of the 19th century. The molecular existence was considered unproven and the molecular hypothesis unnecessary. At the time van der Waals' thesis was written (1873), the molecular structure of fluids had not been accepted by most physicists, and liquid and vapor were often considered as chemically distinct. But van der Waals's work affirmed the reality of molecules and allowed an assessment of their size and attractive strength. His new formula revolutionized the study of equations of state. By comparing his equation of state with experimental data, Van der Waals was able to obtain estimates for the actual size of molecules and the strength of their mutual attraction. [5] The effect of Van der Waals's work on molecular physics in the 20th century was direct and fundamental. [6] By introducing parameters characterizing molecular size and attraction in constructing his equation of state, Van der Waals set the tone for modern molecular science. That molecular aspects such as size, shape, attraction, and multipolar interactions should form the basis for mathematical formulations of the thermodynamic and transport properties of fluids is presently considered an axiom. [7] With the help of the van der Waals's equation of state, the critical-point parameters of gases could be accurately predicted from thermodynamic measurements made at much higher temperatures. Nitrogen, oxygen, hydrogen, and helium subsequently succumbed to liquefaction. Heike Kamerlingh Onnes was significantly influenced by the pioneer work of van der Waals. In 1908, Onnes became the first to make liquid helium; this led directly to his 1911 discovery of superconductivity. [8]

An ideal gas is a theoretical gas composed of many randomly moving point particles whose only interactions are perfectly elastic collisions. The ideal gas concept is useful because it obeys the ideal gas law, a simplified equation of state, and is amenable to analysis under statistical mechanics.

Ernst Waldfried Josef Wenzel Mach was an Austrian physicist and philosopher, noted for his contributions to physics such as study of shock waves. The ratio of one's speed to that of sound is named the Mach number in his honor. As a philosopher of science, he was a major influence on logical positivism and American pragmatism. Through his criticism of Newton's theories of space and time, he foreshadowed Einstein's theory of relativity.

Friedrich Wilhelm Ostwald was a German chemist. He received the Nobel Prize in Chemistry in 1909 for his work on catalysis, chemical equilibria and reaction velocities. Ostwald, Jacobus Henricus van 't Hoff, Walther Nernst, and Svante Arrhenius are usually credited with being the modern founders of the field of physical chemistry.

Van der Waals started his career as a school teacher. He became the first physics professor of the University of Amsterdam when in 1877 the old Athenaeum was upgraded to Municipal University. Van der Waals won the 1910 Nobel Prize in physics for his work on the equation of state for gases and liquids. [9]

Physics is the natural science that studies matter, its motion, and behavior through space and time, and that studies the related entities of energy and force. Physics is one of the most fundamental scientific disciplines, and its main goal is to understand how the universe behaves.

The University of Amsterdam is a public university located in Amsterdam, Netherlands. The UvA is one of two large, publicly funded research universities in the city, the other being the VU University Amsterdam (VU). Established in 1632 by municipal authorities and later renamed for the city of Amsterdam, the University of Amsterdam is the third-oldest university in the Netherlands. It is one of the largest research universities in Europe with 31,186 students, 4,794 staff, 1,340 PhD students and an annual budget of €600 million. It is the largest university in the Netherlands by enrollment. The main campus is located in central Amsterdam, with a few faculties located in adjacent boroughs. The university is organised into seven faculties: Humanities, Social and Behavioural Sciences, Economics and Business, Science, Law, Medicine, and Dentistry.

## Biography

### Early years and education

Johannes Diderik van der Waals was born on 23 November 1837 in Leiden in the Netherlands. He was the eldest of ten children born to Jacobus van der Waals and Elisabeth van den Berg. His father was a carpenter in Leiden. As was usual for working-class children in the 19th century, he did not go to the kind of secondary school that would have given him the right to enter university. Instead he went to a school of “advanced primary education”, which he finished at the age of fifteen. He then became a teacher's apprentice in an elementary school. Between 1856 and 1861 he followed courses and gained the necessary qualifications to become a primary school teacher and head teacher.

Leiden is a city and municipality in the province of South Holland, Netherlands. The municipality of Leiden had a population of 123,856 in August 2017, but the city forms one densely connected agglomeration with its suburbs Oegstgeest, Leiderdorp, Voorschoten and Zoeterwoude with 206,647 inhabitants. The Netherlands Central Bureau of Statistics (CBS) further includes Katwijk in the agglomeration which makes the total population of the Leiden urban agglomeration 270,879, and in the larger Leiden urban area also Teylingen, Noordwijk, and Noordwijkerhout are included with in total 348,868 inhabitants. Leiden is located on the Oude Rijn, at a distance of some 20 kilometres from The Hague to its south and some 40 km (25 mi) from Amsterdam to its north. The recreational area of the Kaag Lakes (Kagerplassen) lies just to the northeast of Leiden.

In 1862, he began to attend lectures in mathematics, physics and astronomy at the University in his city of birth, although he was not qualified to be enrolled as a regular student in part because of his lack of education in classical languages. However, the University of Leiden had a provision that enabled outside students to take up to four courses a year. In 1863 the Dutch government started a new kind of secondary school (HBS, a school aiming at the children of the higher middle classes). Van der Waals—at that time head of an elementary school—wanted to become a HBS teacher in mathematics and physics and spent two years studying in his spare time for the required examinations.

A classical language is a language with a literature that is classical. According to UC Berkeley linguist George L. Hart, "it should be ancient, it should be an independent tradition that arose mostly on its own, not as an offshoot of another tradition, and it must have a large and extremely rich body of ancient literature."

In 1865, he was appointed as a physics teacher at the HBS in Deventer and in 1866, he received such a position in The Hague, which was close enough to Leiden to allow van der Waals to resume his courses at the University there. In September 1865, just before moving to Deventer, van der Waals married the eighteen-year-old Anna Magdalena Smit.

### Professorship

Van der Waals still lacked the knowledge of the classical languages that would have given him the right to enter university as a regular student and to take examinations. However, it so happened that the law regulating the university entrance was changed and dispensation from the study of classical languages could be given by the minister of education. Van der Waals was given this dispensation and passed the qualification exams in physics and mathematics for doctoral studies.

At Leiden University, on June 14, 1873, he defended his doctoral thesis Over de Continuïteit van den Gas- en Vloeistoftoestand (on the continuity of the gaseous and liquid state) under Pieter Rijke. In the thesis, he introduced the concepts of molecular volume and molecular attraction. [10]

In September 1877 van der Waals was appointed the first professor of physics at the newly founded Municipal University of Amsterdam. Two of his notable colleagues were the physical chemist Jacobus Henricus van 't Hoff and the biologist Hugo de Vries. Until his retirement at the age of 70 van der Waals remained at the Amsterdam University. He was succeeded by his son Johannes Diderik van der Waals, Jr., who also was a theoretical physicist. In 1910, at the age of 72, van der Waals was awarded the Nobel Prize in physics. He died at the age of 85 on March 8, 1923.

## Scientific work

The main interest of van der Waals was in the field of thermodynamics. He was influenced by Rudolf Clausius' 1857 treatise entitled Über die Art der Bewegung, welche wir Wärme nennen (On the Kind of Motion which we Call Heat). [11] [12] Van der Waals was later greatly influenced by the writings of James Clerk Maxwell, Ludwig Boltzmann, and Willard Gibbs. Clausius' work led him to look for an explanation of Thomas Andrews' experiments that had revealed, in 1869, the existence of critical temperatures in fluids. [13] He managed to give a semi-quantitative description of the phenomena of condensation and critical temperatures in his 1873 thesis, entitled Over de Continuïteit van den Gas- en Vloeistoftoestand (On the continuity of the gas and liquid state). [14] This dissertation represented a hallmark in physics and was immediately recognized as such, e.g. by James Clerk Maxwell who reviewed it in Nature [15] in a laudatory manner.

In this thesis he derived the equation of state bearing his name. This work gave a model in which the liquid and the gas phase of a substance merge into each other in a continuous manner. It shows that the two phases are of the same nature. In deriving his equation of state van der Waals assumed not only the existence of molecules (the existence of atoms was disputed at the time [16] ), but also that they are of finite size and attract each other. Since he was one of the first to postulate an intermolecular force, however rudimentary, such a force is now sometimes called a van der Waals force.

A second great discovery was published in 1880, when he formulated the Law of Corresponding States. This showed that the van der Waals equation of state can be expressed as a simple function of the critical pressure, critical volume, and critical temperature. This general form is applicable to all substances (see van der Waals equation.) The compound-specific constants a and b in the original equation are replaced by universal (compound-independent) quantities. It was this law which served as a guide during experiments which ultimately led to the liquefaction of hydrogen by James Dewar in 1898 and of helium by Heike Kamerlingh Onnes in 1908.

In 1890, van der Waals published a treatise on the Theory of Binary Solutions in the Archives Néerlandaises. By relating his equation of state with the Second Law of Thermodynamics, in the form first proposed by Willard Gibbs, he was able to arrive at a graphical representation of his mathematical formulations in the form of a surface which he called Ψ (Psi) surface following Gibbs, who used the Greek letter Ψ for the free energy of a system with different phases in equilibrium.

Mention should also be made of van der Waals' theory of capillarity which in its basic form first appeared in 1893. [17] In contrast to the mechanical perspective on the subject provided earlier by Pierre-Simon Laplace, [18] van der Waals took a thermodynamic approach. This was controversial at the time, since the existence of molecules and their permanent, rapid motion were not universally accepted before Jean Baptiste Perrin's experimental verification of Albert Einstein's theoretical explanation of Brownian motion.

### Personal life

He married Anna Magdalena Smit in 1865, and the couple had three daughters (Anne Madeleine, Jacqueline E. van der Waals  (nl ), Johanna Diderica) and one son, the physicist Johannes Diderik van der Waals, Jr.  (nl ) Jacqueline was a poet of some note. Van der Waals' nephew Peter van der Waals was a cabinet maker and a leading figure in the Sapperton, Gloucestershire school of the Arts and Crafts movement. The wife of Johannes van der Waals died of tuberculosis at 34 years old in 1881. After becoming a widower Van der Waals never remarried and was so shaken by the death of his wife that he did not publish anything for about a decade. He died in Amsterdam on March 8, 1923, one year after his daughter Jacqueline had died.

His grandson, Christopher D. Vanderwal is a distinguished professor of Chemistry at the University of California, Irvine.

## Honors

Van der Waals received numerous honors and distinctions, besides winning the 1910 Nobel Prize in Physics. He was awarded an honorary doctorate of the University of Cambridge; was made honorary member of the Imperial Society of Naturalists of Moscow, the Royal Irish Academy and the American Philosophical Society; corresponding member of the Institut de France and the Royal Academy of Sciences of Berlin; associate member of the Royal Academy of Sciences of Belgium; and foreign member of the Chemical Society of London, the National Academy of Sciences of the U.S., and of the Accademia dei Lincei of Rome. Van der Waals was a member of the Koninklijke Nederlandse Akademie van Wetenschappen (Royal Netherlands Academy of Sciences) since 1875. [19] From 1896 until 1912, he was secretary of this society.

## Related Research Articles

Professor Heike Kamerlingh Onnes FRSFor HFRSE FCS was a Dutch physicist and Nobel laureate. He exploited the Hampson–Linde cycle to investigate how materials behave when cooled to nearly absolute zero and later to liquefy helium for the first time, in 1908. He was also the discoverer of superconductivity in 1911.

The van der Waals radius, rw, of an atom is the radius of an imaginary hard sphere representing the distance of closest approach for another atom. It is named after Johannes Diderik van der Waals, winner of the 1910 Nobel Prize in Physics, as he was the first to recognise that atoms were not simply points and to demonstrate the physical consequences of their size through the van der Waals equation of state.

Leiden University, founded in the city of Leiden, is the oldest university in the Netherlands. The university was founded in 1575 by William, Prince of Orange, leader of the Dutch Revolt in the Eighty Years' War. The Dutch Royal Family and Leiden University have a close association: Queen Juliana, Queen Beatrix and King Willem-Alexander are former students. The university came into particular prominence during the Dutch Golden Age, when scholars from around Europe were attracted to the Dutch Republic due to its climate of intellectual tolerance and Leiden's international reputation. During this time Leiden was home to such figures as René Descartes, Rembrandt, Christiaan Huygens, Hugo Grotius, Baruch Spinoza and Baron d'Holbach.

Willem Hendrik Keesom was a Dutch physicist who, in 1926, invented a method to freeze liquid helium. He also developed the first mathematical description of dipole–dipole interactions in 1921. Thus, dipole–dipole interactions are also known as Keesom interactions. He was previously a student of Heike Kamerlingh Onnes, who had discovered superconductivity.

Pieter Zeeman was a Dutch physicist who shared the 1902 Nobel Prize in Physics with Hendrik Lorentz for his discovery of the Zeeman effect.

At standard pressure, the chemical element helium exists in a liquid form only at the extremely low temperature of −270 °C. Its boiling point and critical point depend on which isotope of helium is present: the common isotope helium-4 or the rare isotope helium-3. These are the only two stable isotopes of helium. See the table below for the values of these physical quantities. The density of liquid helium-4 at its boiling point and a pressure of one atmosphere is about 0.125 grams per cm3, or about 1/8th the density of liquid water.

The year 1873 in science and technology involved some significant events, listed below.

The ideal gas law can be stated in terms of the compressibility factor Z:

Wander Johannes de Haas was a Dutch physicist and mathematician. He is best known for the Shubnikov–de Haas effect, the de Haas–van Alphen effect and the Einstein–de Haas effect.

Johannes Bosscha Jr. was a Dutch physicist.

Petrus Leonardus Rijke was a Dutch physicist, and a professor in experimental physics at the University of Leiden. Rijke spent his scientific career exploring the physics of electricity, and is known for the Rijke tube. On July 1, 1852 he was married to Johanna Hamaker. They had 6 sons and 6 daughters.

According to van der Waals, the theorem of corresponding states indicates that all fluids, when compared at the same reduced temperature and reduced pressure, have approximately the same compressibility factor and all deviate from ideal gas behavior to about the same degree.

The van der Waals surface of a molecule is an abstract representation or model of that molecule, illustrating where, in very rough terms, a surface might reside for the molecule based on the hard cutoffs of van der Waals radii for individual atoms, and it represents a surface through which the molecule might be conceived as interacting with other molecules. Also referred to as a van der Waals envelope, the van der Waals surface is named for Johannes Diderik van der Waals, a Dutch theoretical physicist and thermodynamicist who developed theory to provide a liquid-gas equation of state that accounted for the non-zero volume of atoms and molecules, and on their exhibiting an attractive force when they interacted. van der Waals surfaces are therefore a tool used in the abstract representations of molecules, whether accessed, as they were originally, via hand calculation, or via physical wood/plastic models, or now digitally, via computational chemistry software. Practically speaking, CPK models, developed by and named for Robert Corey, Linus Pauling, and Walter Koltun, were the first widely used physical molecular models based on van der Waals radii, and allowed broad pedagogical and research use of a model showing the van der Waals surfaces of molecules.

Johannes Petrus Kuenen was a Dutch physicist.

Sir John Shipley Rowlinson was a British chemist. He attended Oxford University where he completed his undergraduate studies in 1948 and doctoral in 1950. He then became research associate at University of Wisconsin (1950–1951), lecturer at University of Manchester (1951–1961), Professor at Imperial College London (1961–1973) and back at Oxford from 1974 to his retirement in 1993.

Maxwell’s thermodynamic surface is an 1874 sculpture made by Scottish physicist James Clerk Maxwell (1831–1879). This model provides a three-dimensional space of the various states of a fictitious substance with water-like properties. This plot has coordinates volume (x), entropy (y), and energy (z). It was based on the American scientist Josiah Willard Gibbs’ graphical thermodynamics papers of 1873. The model, in Maxwell's words, allowed "the principal features of known substances [to] be represented on a convenient scale."

Cornelis Jacobus (Cor) Gorter was a Dutch experimental and theoretical physicist. Among other work, he discovered paramagnetic relaxation and was a pioneer in low temperature physics.

## References

This article incorporates material from the Citizendium article "Johannes Diderik van der Waals", which is licensed under the Creative Commons Attribution-ShareAlike 3.0 Unported License but not under the GFDL.
1. Every word in isolation: .
2. Parsegian, V. Adrian (2005). Van der Waals Forces: A Handbook for Biologists, Chemists, Engineers, and Physicists. (Cambridge University Press), p. 2. “The first clear evidence of forces between what were soon to be called molecules came from Johannes Diderik van der Waals' 1873 Ph.D. thesis formulation of the pressure p, volume V, and temperature T of dense gases.”
3. van der Waals; J. D. (1873). Over de continuiteit van den gas- en vloeistoftoestand (On the Continuity of the Gaseous and Liquid States) (doctoral dissertation). Universiteit Leiden.
4. Sengers, Johanna Levelt (2002), p. 16
5. Kipnis, A. Ya.; Yavelov, B. E.; Rowlinson, J. S.: Van der Waals and Molecular Science. (Oxford: Clarendon Press, 1996)
6. Sengers, Johanna Levelt (2002), p. 255-256
7. Blundell, Stephen: Superconductivity: A Very Short Introduction. (Oxford University Press, 1st edition, 2009, p. 20)
8. "The Nobel Prize in Physics 1910". Nobel Foundation. Retrieved 2008-10-09.
9. see the article on the van der Waals equation for the technical background
10. J.D. van der Waals, 1910, "The equation of state for gases and liquids," Nobel Lectures in Physics, pp. 254-265 (December 12, 1910), see , accessed 25 June 2015.
11. Clausius, R. (1857). "Über die Art der Bewegung, welche wir Wärme nennen". Annalen der Physik . 176 (3): 353–380. Bibcode:1857AnP...176..353C. doi:10.1002/andp.18571760302.
12. Andrews, T. (1869). "The Bakerian Lecture: On the Gaseous State of Matter". Philosophical Transactions of the Royal Society of London. 159: 575–590. doi:10.1098/rstl.1869.0021.
13. van der Waals, JD (1873) Over de Continuiteit van den Gas- en Vloeistoftoestand (on the continuity of the gas and liquid state). PhD thesis, Leiden, The Netherlands.
14. Maxwell, J.C. (1874). "Van der Waals on the Continuity of Gaseous and Liquid States". Nature. 10 (259): 477–480. Bibcode:1874Natur..10..477C. doi:10.1038/010477a0.
15. Tang, K.-T.; Toennies, J. P. (2010). "Johannes Diderik van der Waals: A Pioneer in the Molecular Sciences and Nobel Prize Winner in 1910". Angewandte Chemie International Edition. 49: 9574–9579. doi:10.1002/anie.201002332. PMID   21077069.
16. van der Waals, J.D. (1893). "Thermodynamische theorie der capillariteit in de onderstelling van continue dichtheidsverandering". Verhand. Kon. Akad. V Wetensch. Amst. Sect. 1 (Dutch; English translation in J. Stat. Phys., 1979, 20:197).
17. Laplace, P.S. (1806). Sur l'action capillaire (Suppl. au livre X, Traité de Mécanique Céleste). Crapelet; Courcier; Bachelier, Paris.
18. "Johannes Diderik van der Waals Senior (1837 - 1923)". Royal Netherlands Academy of Arts and Sciences. Retrieved 17 July 2015.
• Kipnis, A. Ya.; Yavelov, B. E.; Rowlinson, J. S.: Van der Waals and Molecular Science. (Oxford: Clarendon Press, 1996, 313pp) ISBN   0-19-855210-6
• Sengers, Johanna Levelt: How Fluids Unmix: Discoveries by the School of Van der Waals and Kamerlingh Onnes (Edita - History of Science and Scholarship in the Netherlands). (Edita-the Publishing House of the Royal, 2002, 318pp)
• Shachtman, Tom: Absolute Zero and the Conquest of Cold. (Boston: Houghton Mifflin, 1999)
• Van Delft, Dirk: Freezing Physics: Heike Kamerlingh Onnes and the Quest for Cold. (Edita-the Publishing House of the Royal, 2008, 592pp)
• Van der Waals, J. D.: Edited and Intro. J. S. Rowlinson: On the Continuity of the Liquid and Gaseous States. (New York: Dover Publications, 2004, 320pp)