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 Section lll: Growth of face and
craniofacial complex

7. Development of teeth, dentition e

and occlusion (e-only) ................109
Section l: Historical aspects of A. Mathur, S.S. Rana, O.P. Kharbanila
orthodontics: ancient, yesteryears,
yesterdays, today and tomorrow 8. Prenatal development of the foetus e
concerning the craniofacial
region (e-only)....... ......................111
1.1. History of dentistry and significant events that Neeraj Wadhawan, Ram S. Nanda,
revolutionised dentistry ................3 O.P. Khqrbanda
O.P. Kharbanda

1.2. History of orthodontics.................................... 9

9. Concepts of growth and development ..........113
O.P. Kharbanda, Neeraj Wadhawan,
1.3. History of orthodontic speciality in India .....22 Ram S. Nanda

10. Postnatal growth of face and craniofacial

Section ll: Fundamentals of orthodontics region......... ............. 133
O.P. Kharbanda, Ram S. Nanda,
2. Adverse consequences of malocclusion Neeraj Wadhawtn
and benefits of orthodontic treatment........... 35
'11. Functions of stomatognathic system
O.P. Kharbanda
and their implications on occlusion .............151
3. Epidemiology of malocclusion O.P. Kharbanda, Shailendra Singh Rana,
and orthodontic treatment needs.................... 5l Anurag Gupta
O.P. Kharbanda

4. Classification and methods of recording

malocclusion ................ ...............62 Section lV: Orthodontic diagnosis
O.P. Kharbanda

5. Recording the severity of malocclusion: 12. Clinical evaluation.. ................... 169

orthodontic indices .....................85 O.P. Kharbanda
O.P. Kharbanda
13. Diagnostic records and their evaluation...... 195
6. Psychological implications of malocclusion
O.P. Kharbanda
and orthodontic treatment............................. 99
O.P. Kharbqnda, Rajesh Sagar 14. Practical clinical photography................. ......279
Ahhter Husain
 Contents

29. Three-dimensional imaging in

Section V: Radiation and non-radiation
orthodontics ................. ............. 369
imaging in orthodontics
O.P. Kharbanda, Sunil D. Kapila,
Rajiv Balachandran
15. Cephalometrics: historical perspectives,
methods and Iandmarks.............. ..,.,............ 233 30. Three-dimensional cephalometry................. 387
Rajiu Balachandran, Abhisheh Gupta,
O.P. Kharbanda
Viren Sardana, O.P. Kharbanda
16. Downs'analysis ......249
O.P. Kharbanda
31. 3D volumetric analysis, and clinical o
implications of the upper airway and
17. Tweed's analysis...... ...................253 sinuses (e-only) .......4O3
O.P. Kharbanda Bala Chakrauarthy Neelapu, Harish K Sarilana,
18. Steiner's analysis...... ..................257 Rajiu Balachandran, O.P. Kharbanda, Karthik S
O.P. Kharbanda

'19. Ricketts' l2-factor analysis ........263 Section Vll: Removable orthodontic

O.P. Kharbanda appliances
20. Vertical linear dimensions of face
and Sassouni's analysis ..............221 32. Role of removable appliances
O.P. Kharbanda
in contemporary orthodontics ..................... 4O7
z',t. Cephalometric analysis of the soft tissue O.P. Kharbanda
of the face ............ ...222 33. Invisible removable appliances: The Clear
O.P. Kharbanda
Aligners..... ..............423
22. Posteroanterior cephalometric analysis ....... 289 Maria Orellana Valvekens
O.P. Kharbanda

23. Interpretation and clinical applications

Section Vlll: Orthodontic armamentarium
of cephalometric data in diagnosis,
treatment planning and prognosis................301
O.P. Kharbanda, Rajiu Balachandrqn 34. Concept of orthodontic operatory
design (e-only)
e
........437
24. Lateral, PA and 3D Cephalometric
Prabhat Kumar Chaudhai, O.p. Kharbanda
superimposition ........... ..............311
O.P. Kharbanda 35. Instruments and equipment
in orthodontic use (e-only)
e
........439
25. Errors in cephalometrics .............................. 329
Prabhat Kumar Chaudhari, O.p. Kharbsnda
O.P. Kharbanda
35. Components of fixed orthodontic E
appliance ........,........441
Section Vl: Digital orthodontics O.P. Kharbands

37. Orthodontic archwires: material and their

E ZO. Digital and computerised cephalometrics...33g properties.. .............. 459
O.P. Kharbanda O.P. Kharbanila, Anurag Gupta
27. 3D data acquisition and 38. Rubber and synthetic elastic accessories. ..... 472
orthodontic triad........... ............34g O.P. Kharbanila
Rajiu Balachandran, O.p. Kharbanila
39. Bonding orthodontic appliances.................. 4g5 E
E ZA. 3D digital models ...352 O.P. Kharbanda, Priyanha Kapoor,
O.P. Kharbanila, Rajiv Balachandran Anurag Gupta

xvi
 Contents

Section lX: Contemporary orthodontic Section Xl: Class ll malocclusion

treatment
50. Class II division I malocclusion: features
40. The biological basis for orthodontic and early intervention of grorving maxillary
tooth movement.......... .............. 505 excess ...737
Vinod Krishnan O.P. Kharbanda

41. Principles of biomechanics and appliance 51. Evolution of functional appliances

design......... ..............519 and treatment with one piece removable
Varun Kalra appliances. ..............753
O.P. Kharbanda
42. Preservation of normal occlusion and
interception of malocclusion during 52. Treatment approaches with twin block E
early mixed dentition .................531 appliance ................767
O.P. Kharband& O.P. Kharbanda

43. Orthodontic treatment with contemporary 53. Interception and treatment of mandibular
fixed appliance Phase I: laying the retrusion with non-compliant fixed
foundation. .............549 functional appliances ................809
O.P. Kharbanda O.P. Kharbanda

44. Anchorage in orthodontic practice............... 563 54. Mode of action of functional appliances.....827
O.P. Kharbanda O.P. Kharbanda

E 4s. Tweed philosophy, biomechanics 55. Dentofacial orthopaedics for class II

and principles of treatment.............. .............571 malocclusion with vertical maxillary
O.P. Kharbanda, Mugdha Mankar excess ...837
O.P. Kharbando
E 46. Orthodontic treatment with contemporary
fixed appliance Phase II: maior tooth 55. Management of class II malocclusion
movements ..............607 with fixed appliance ...................851
O.P. Kharbanda O.P. Kharbanda

47. The pre-adjusted edgewise appliance ........... 645 57. Class II division 2 malocclusion.................. 865
O.P. Kharbanda O.P. Kharbanda

48. Orthodontic treatment with self-ligating

bracket systems...... .................... 669 Section Xll: Class lll malocclusion
Shailesh Deshmukh, Vilas Samrit,
O.P. Kharband&
58. Class III malocclusion in growing children..88l
MA Darendeliler, O.P. Kharbanda, S. Karthih

Section X: Non-extraction treatment 59. Orthodontic treatment of borderline

class III malocclusion .................................... 91 Z
Gauri Vichare, O.P. Kharbanda
49.1. Non-extraction treatment with maxillary
expansion and interproximal reduction ...... 68z
O.P. Kharbandu
Section Xlll: Newer trends
in orthodontics
49.2. Non-extraction treatment with non-compliance
molar distalisation ..................... 711
O.P. Kharbanda
60. Temporary anchorage devices....................... 935 E}
O.P. Kharbanda, Vilas Samrit

xvtl
 Contents

61. Surgically facilitated rapid tooth 71. Asymmetry of occlusion ...........1085 ,

movement (SF-RTM).... ..............957 O.P. Kharbanda

Priyanka Sethi Kumar, O.P. Kharbanda
72. Cant of occlusal plane in transverse
62. Orthodontic considerations direction ................1097
of inter-disciplinary treatment ......................971 George Anka, O.P. Kharbanda
Parul Taneja, Lohesh Suri
73. Asymmetries of the face (e-only).................. 1115 e
@ os. Evidence-based orthodo ntics (e - only) ........... 9 8f Mithran Goonewarilene, O.P. Kharbanda
NG Tbshniwal
74. Temporomandibular disorders
and orthodontics........... ...........1112
Section XIV: lmpactions Sanjivan Kandasamy, Charles S. Greene,
and transpositions Donald J. Rinchuse

64. Orthodontic aspects of impacted Section XVll: Expanding role of

anterior teeth.......... ................... gg5 orthodontist and inter-disciplinary care
O.P. Kharbanda

65. Transposition of teeth .............. l0ll 75. Inter-disciplinary management

O.P. Kharbanda
of cleft lip and pa1ate......... .......1122
e OO. Auto-transplantation of teeth O.P. Kharbanda, Nitiha Monga
in orthodontic practice (e-only)................... 101 7 76. Orthodontist's roles in upper airway sleep
Rajiu Balachandran, O.P. Kharbanda
disorders.... ............1162
Balakrishnsn I ayan, Abhijeet Kadu,
O.P. Kharbanda

Section XVlll: Steps in conclusion

67. Ortho-surgical management of skeletal of orthodontic therapy
malocclusions............... ............ 1021
O.P. Kharbanda, M. Ali Darendeliler 77. Orthodontic treatment with contemporary
68. Maxillomandibular distraction fixed appliance Phase III: finishing
osteogenesis for orthodontist ..1rO4Z and detaiIing................. ............tl89
Balahrishnan layan, Nand.a Kishore Sahoo, O.P. Kharbanda
Abhijeet Kailu
78. Deband, debracketing and delivery
of reiention appliance ............. l2O5
Section XVI: Treatment of complex O.P. Kharbanda
malocclusions 79. Post-orthodontic care and management
of white spot lesions ................1213
69. Malocclusion and asymmetries of Srideui Psdmanabhan, O.p. Kharbanda
the face...... .............tO62 80. Maintenance of the outcome results,
O.P. Kharbanda retention and relapse ................1219
E zo. Dental midline deviations.. ...... tOTl
O.P. Kharbanda
Prashanti Bollu, O.p. Kharbanda Index ..............1237

xvill
 Section lrl
H istorica I aspects of orthodontics:
a ncient, yesteryea rs, yesterdays,
today and tomorrow

1.1. History of dentistry and significant events that

revolutionised dentistry 3
1.2. History of orthodontics 9
1.3. History of orthodontic speciality in lndia 27
 Chapter 1.1

History of dentistry and signif icant events that

revol ution ised dentistry
A.P. Kharbanda

CHAPTER OUTLINE

The origin of the term Orthodontia 3 Discovery of X-rays 5

Orthodontosie and orthodontia 3 Dentistry in 19th century 5
Orthodontics and dentofacia I orthopaedics 3 Bonding in dentistry 6
Orthodontics and dentofacial deformities 3 High-speed dentistry 6
History of dentistry before Christ was born (BC) 4 Branemark era 6
The beginning of dentistry as a profession: early Dentistry in 20th century 6
to middle ages (AD) 4 Advances in restorative materials 6
The development of dentistry as a science 4 Regenerative dentistry 6
Pierre Fauchard, 'The 5urgeon Dentist' 4 Multi-detector row CT and CBCT 6
World's first dental journal 5
Dentistry in 21st century 8
Professionalisation of dental education 5
Application of 3D technology and CAD-CAM 8
The dental drill 5 Key Points 8

1976by B. F. Dewel, has been added to better describe the

whole compass of an orthodontist's bailiwick.'?

Orthodontosie and orthodontia Orthodontics and dentofacial deformities

The term Orthodontosie was coined by joachim Lefoulon, 'lb represent the extended role of orthodontics in treating and
a Frenchman in 1841, in his book Nouueau traite de l'art contributing to the management of developing and devel-
du dentiste. The term roughly translates into 'Orthodontia'.
oped, mild to complex dentofacial deformities' the Centre for
Ioachim Lefoulon used an elastic gold archwire on the Dental Education and Research at All India Institute of Medi-
palatal side to trear crowding and irregular teeth. The gold
cal Sciences chaired by Professor O.p. Kharbanda preferred to
arch piano wire exerted shaping effect on alveolar process
use the term Orthodontics and Dentofacial Deformities. The
and spring effect on teeth, which is an essential concept of
term Dentofacial Deformities was coined to be added with or-
orthodontics.'
thodontics to avoid confusion for medical professionals, who
considered dentofacial orthopaedics qmonyrnous to maxillo-
Orthodontics and dentofacial orthopaedics facial trauma and referred jaw fracture patients to the ortho-
dontic department. The first textbook, with the title Diagnosis
An English philologist, Sir lames Murray ( 1909), realised that and Management of Malocclusion and Dentofacial Deformities,
the suf6x 'ia' appropriately referred to a medical condition was published by Elsevier India in 2009.
(e.g. amnesia) and suggested the term orthodontics. It took The story of orthodontics and its development is closely
manyyears, till 1930s, before the term Orthodontics was used linked to the history of dentistry. Here are some notable
by professionals.'Dentofacial Orthopaedics', suggested in excerpts.
@|r|Historica|aspectsoforthodontics:ancient,yesteryears,yesterdays,todayandtomorrow
eventually killed hirn was found. Fortunately, they continued
History of dentistry before Christ to advance in dentistry and in 100 B(,, Celsus, a Ronlan medi-
was born (BC) cal r,r'riter, described oral h1'giene, and rnethocls to stabilise
teeth, as well as how to treat toothaches, teething pain, and
Historical evidence on dental ailments and descriptions can iaw fractures.8
be found in Indus valley, Greece, and Egyptian civilisations.
The Indus Valley Civilisation has yielded evidence for the
earliest form of dentistry which dates back to 7000 BC. The The beginning of dentistry as a profession:
oldestproof of a dental fillingwas found in 2OI2in Slovenia. A early to middle ages (AD)
6,500-year-old jawbone demonstrated a deep cavity impacting
the dentin layer of the tooth which was packed with beeswax.3'o
The Etruscans prepared crowns and fixed bridgework with
5000 BC. Tooth decay was thought to have been caused by
gold. A medical text in China mentions the use of 'silver
worrns and this belief continued to prevail as late as 1300s. Dur-
paste', a type of amalgam for filling cavities in teeth sometime
ing these years a French surgeon, Guy de Chauliac, continued to
promote the belief that worrns caused tooth decay. in 700 AD.
2600 BC. The earliest known reference to a person identi- In 1530, l.rtzney Buchlein published The Linle Medicinal
Book for All Kinds of Dkeases and Infirmities of the Teeth, the first
fied as a dental practitioner was the description on the tomb
built following the death of Hesy-Re, an Egyptian scribq book devoted entirely to dentistry in Germany. The tart was
called the first 'dentist'. An inscription on his tomb includes written for barbers and surgeons who treated diseases of the
the title'the greatest of those who deal with teeth, and of phy- mouth.
sicians'. The Egyptians bound replacement teeth together with
In 1575, Ambroise Pare, famous French surgeon, published
gold wires (Fig. 1.1.1A ). his Compleu Worlu. His text included practical information
1700-f 550 BC. The Ebers papyrus, the ancient medical trea- about dentistry such as tooth extraction and the treatment of
tise written sometime before 3000 BC, provides detailed advice tooth decay and jaw fractures.
on treating wounds in the mouth. Of the 11 recipes, which per-
tain to oral issues, 4 relate to remedies for loose teeth.n'6
700 BC. Pre-Roman Civilization: The Etruscans (a pre-Ro-
man civilisation in Italy) travelled far across seas and gathered
new information. Both human and animal teeth were used as
the first prosthetics, beginning around 700 BC? (Fig. 1.1.1B).
Pierre Fauchard, 'The Surgeon Dentist'
500-300 BC. Creek and Roman Dentistry: Around 500- Pierre Fauchard, a French surgeon (Fig. 1.1.2A), published The
300 BC, both Hippocrates and Aristotle wrote about dentistry Surgeon Dentist, A Tieatise on Teeth (Le Chirurgien Dentiste) in
including how teeth erupt, treatment of cavities, gum disease, 1723. Dr Pierre Fauchard is credited as being the Father of
extraction, and even an early form of orthodontics involving Modern Dentistry because his book was the first to describe
the use of wire to help secure loose teeth. a comprehensive system for the practice of dentistry includ-
At the same time, one ancient Greek mummy, with a mouth ing basic oral anatomy and function, operative and restorative
full of cavities, such that it caused a sinus infection which techniques, and denture construction.

* --l-
, ,.h4* ffi
t,;lt"ui
,,
"''
!

* t

(B)

Figure 1'1'1 (A, B). This image is from The National Museum of Dentistry in Baltimore. The "treatment,,
in the mandible shown here was done at the
turn of the 20th century. Vincenzo Guerini, who wrote A History of Dentistry and who made models
of ancient dentistry examples which he supposedly
saw in his travels to Egypt rhe Egyptian mummy was supposedly 2000 years old. Source:
https://commons.wikimedia.org/wikilFile:Ancient_Egypt_Den-
tistry.jpg, https://de.wikipedia.org/wiki/Datei:Ancient_Egypt_Dentistry2.jpg

4
 Historyofdentistryandsignificanteventsthatrevo|utioniseddentistry@t'''|l
In 1746, Dr Claude Mouton was the first to suggest gold
crown and post to be retained in the root canal. The first
commercial production of non-metal porcelain teeth was
introduced by Samuel Stockton (1825). His S.S. White Den-
tal Manufacturing Company supplied commercially manu-
factured porcelain teeth and established and dominated the
dental supply market throughout the 19th century.

World's first dental journal

World's first dental joumal began publication in 1839. It
was named the "American ]ournal of Dental Science". The pro-
cess of mlcanisation invented by Charles Goodyear during
the same years greatly influenced the dental profession owing
to low cost, and ease of moulding rubber to the mouth. The
vulcanised rubber soon became the denture base material of
choice for making false teeth. In 1864, the moulding process
for vulcanite dentures was patented; that meant an onerous li-
censing fee. Dental profession continued to fight it for the next
25 years.

Professionalisation of dental education

The opening of the first dental school with DDS (Doctor of
Dental Surgery) degree in 1840 at Baltimore, USA, marked
the professionalisation of dental education. The Baltimore
College of Dental Surgery was founded by Horace HMen
and Chapin Harris in 1840 and this School awarded the
first professional dental school degree, the DDS degree. This
school later merged with the Llniversity of Maryland in 1923.
The American Society of Dental Surgeons, the world's first na-
tional dental organisation, was also founded in 1840 and was
dissolved in 1856.
Between 1845 and the turn of the 19th century major in-
ventions in chemistry and physics changed the world of medi-
cine and dentistry like the successful demonstration of tooth
extraction using ether, discovery ofX-rays and synthesis oflo-
cal anaesthesia. The dental drills, foot engine and electric drill
were discovered during this time.
In 1845, Dr Horace Wells, a dentist had conducted a dem-
onstration of dental extraction under general anaesthesia
with nitrous oxide, the laughing gas, but it was regarded a fail-
r--_r
ure when the patient cried out. A year later, in 1846, another
dentist, William Morton, conducted the first successful public
demonstration of the use of ether anaesthesia for surgery.
fiEure'l "1.? (A) Perre Faucharrl the Father of Modern Dentstry (1678
The dental drill March22, 1761 ) (B) Prototype of bandeau used to al qn teeth byty nq them
on rgid plate. Reproduced vttth pcrnssron. Source ttt/ahl N arthoclontics
The first dental drill, the foot engine was firsr commercially in 3 millennia. Chapt-.r 1; Antrquity to the mrd 1gth century. An I Orthod
manufactured as a foot-treadle dental engine under patent by Dentofacial Orthap. 2005 Feb, 1 27(2).255-9.
lames B. Morrison in 1871. Morrison's inexpensive, mecha-
nised tool supplied with dental burs with enough speed to
cut enamel and dentin smoothly and quickly, revolutionising dertt;rl X-ray of ir living person itr LISA rvirs taken in 1E9(r bv a
the practice of dentistry (Fig. 1.1.3). Much later, anAmerican, pronrirrent Ner,r, ()rleans dentist, C. Edrntrnd Kells.
Ceorge F. Creen, received a patent for the first electric dental
engine, a self-contained motor and handpiece (Fig. 1.1.4).

Dentistry in 19th century

Discovery of X-rays
Wilhelm Roentgen, a German physicist, in 1885, discovered Nineteenth century witnessed major changes with scientific
X-rays which had a great impact on medical practice. The 6rst discovery of formulation of local anaesthesia, the first bonding
 Section Irl

tl
@
{b'
Figure 1.1.3 First foot dental drill was commercially available in
1871. This foot engine is a proud possession of the author who
All Cord'Ifue
the Riltcr I)ental €ngiu

Figure '1.1.4 The dental electric drill that revolutionised restorative

dentistry. (http://mcnygeneatogy.com/pics/picture.php?/21 3lcateqories).
used it in 70s as a dental student.

system, the acid etch, high-speed air drills and the mosr
technology. The first commercial home tooth bleaching prod-
significant being the concept ofosseointegration. In 1905, AI_
uct was marketed in 1989.
fred Einhorn, a German chemist, formulated the local anaes_
thetic procaine, later marketed under the trade name Novocain.
Advances in restorative materials
Bonding in dentistry A year larer in 1990, a new era of aesthetic dentistry began
with the introduction of tooth-corour restorative materiils,
Oskar Hagger, a Swiss chemist, developed the first system of
veneers/ increased usage ofbleaching, and implants. ln 1992,
bonding acrylic resin to dentin in 1949 and a few years larer,
FDA (Food and Drug Administration) approved the erbium
in 1 955, a simple method of increasing the adhesion of acryl_
YAC laser, the first for use on dentin, to treat tooth decay.
ic fillings to enamel was described by Michael Buonocore us_
The need for broad research base in dentistry led to
ing acid etch technique.
renaming The National Institute of Dental Research, to
'National Institute of Dental and Craniofacial Research,.
High-speed dentistry in
1 998.
iohn Borden (1952) first inrroduced a high_speed air_driven con_
tra-angle handpiece. The Airotor attained speed up to 300,000 Regenerative dentistry
rotations per minute and was an immediate commercial success,
launching a new era of high-speed dentisuye,r,, (Box 1.1.1 By 2000, regenerative dentistry and stem cell research,
includ-
). ing banking of primary tooth pulp tissue for regeneration
Branemark era turned out to be the most exciting and promising area
of
dentistry. Regenerating a functional ind living tooth is
The history of modern one of
dentistry will always be remem_ th-e most promising therapeutic strategies forihe
replacement
bered as before and after Branemark era. ln 1980, per_lngvar of a diseased or damaged tooth.il
Branemark described techniques for the osseoinregratioi
of
dental implants and this was perhaps the most thrilling
and
usefirl innovation that had influenced the practice of den"tistry
Multi-detector row CT and CBCT
and patient satisfaction in the century. Discovery of computed tomography added new
dimensions in
maglng of living strucrures. Computed axial tomography
JO_f

Dentistry in 20th Century

The 20th century saw the advances and refinements
in ma_
I {CT), which changed the world of medical imaging nom-ZO
I t"y_r to 3D imaging was invented by British engineer, God_
frey Hounsfield of EMI Laboratories, England and
Africa-born physicist AIan cormack of tifts
sachusetts in 1922. Discovery of cone beam
by South
universiw, Mas-
comput"d i;;;;_
terials, aesthetic dentistry and induction of sophisticated
raphy (CBCT) originated at a small town named
Verona in
6
 History of dentistry and significant events that revolutionised dentistry |11 II
@E
Box 1 .1 .1 Landrnark events in the history of dentistry from FC to 20!0

BC The first and most enduring explanation for what causes tooth decay was the tooth worm, as depicted in the ivory
sculptures, which was first noted by the Surnerians.
2600 BC The earliest known reference to a person identified as a denlal practitioner was the description on the tomb built following
the death of Hesy-Re, an Egyptian scribe, often called the first'dentist'.
1700-1 550 BC The Edwin Smith PapyruVEbers Papyrus is an ancient Egyptian medical text. lt is the oldest known surgical treatise on
trauma. This contains 1 1 recipes, which pertain to oral issues
700 BC Human and animal teeth were used as the first prosthetics, beginning around 700 BC. The Etruscans (a pre-Roman
civilization in ltaly) actually made some basic leaps in dentrstry
500-300 BC Hippocrates and Aristotle wrote about dentistry including how teeth erupt, treatment of cavities, gum disease, extraction,
and even an early form of orthodontics involving the use of wire to help secure loose teeth
166-201 AD The Ftruscans practiced dental prosthetics using gold crowns and fixed bridgework.
700 A medical text in Chrna mentions the use of 'silver paste', a type of amalgam ior filling cavities in teeth.
1210 A Guild of Barbers was established in France.
1530 Artzney Buchletn published The Little Medicinal Book for All Kinds of Diseases and lnfirmities of the Teeth the first book
devoted entirely to dentistry, in Germany.
1575 In France, Ambroise Pare. known as the Father of Surgery, published his Complete Works.
1723 Pierre Fauchard, a French surgeon published The Surgeon Dentist, A Treatise on feeth (Le Chirurgien Dentiste). Surgeon
Pierre Fauchard is credited as being the Father of Modern Dentistry.
1746 Claude Mouton described a gold crown and post to be retained in the root canal.

1825 Samuel Stockton began commercral manufacture of porcelain teeth under 5. S. White Company.
1839 The American Journal of Dental Science, the world s f irst dental journal, began publication.
1840 Horace Hayden and Chapin Harris found the world s first dental school, the Baltimore College of Dental Surgery and
established the Doctor of Dental Surgery (DDS) degree. (The school merged with the University of Maryland in 1923).
1846 Dentist William Morton conducted the first successful public demonstration of the use of ether anaesthesia for surgery.
1871 James B. Morrison patented the first commercially manufactured foot-treadle dental engine.
'1895 Wilhelm Roentgen, a German physicist, discovered the X-ray. In 1896, prominent New Orleans dentist, C. Edmund Kells,
took the first dental X-ray of a living person in the US.
1899 Edward Hartley Angle classified the various forms of malocclusion. Credited with makinq orthodontics into a dental
specialty.
1905 Alfred Finhorn, a German chemist, formulated the local anaesthetic procaine, later marketed under the trade name Novocain.
1955 Michael Buonocore described the acid etch technique, a simple method of increasing the adhesion of acrylic fillings to
enamet.
1957 John Borden introduced a high-speed air-driven contra-angle handpiece. The Airotor obtained speed up to 300,000 rotations
per minute and was an immediate commercial success, launching a new era of high-speed dentistry
1980 Per-lngvar Branemark described techniques for the osseointegration of dental implants
1990 New tooth-coloured restorative materials plus increased usage of bleaching, veneers, and implants inaugurated an era of
aesthetic dentistry.
1972, 1988, 1996 Discovery of multi-detector row CT (MDCT) added new dimensions in 3D imaging of living structures. Computed axial
tomography (CT) was invented in 1972 by British engineer, Godfrey Hounsfield of EMI Laboratories, England and by South
Africa-born physicist, Allan Cormack of Tufts University, Massachusetts. Discovery of CBCT originated at a small town named
Verona in ltaly in 1988. The NewTom or maxiscan was the first CBCT system in the world, installed in 1996.
1990 .... First dental CAD-CAM was invented in Zurich by Siemens and sold by SIRONA.
1997 FDA approved the erbium YAG laser, the first for use on dentin, to treat tooth decay.
'1998 National Institute of Dental Research was renamed National Institute of Dental and Craniofacial Research to more accuratelv
reflect the broad research base.
2000.... Regenerative dentrstry and stem cell research including banking of primary tooth pulp tissue for regeneration, proposeg rn
the new millennium.
2010 3D printing in dentistry oral and maxillofacial surgery and orthodontics.
 Section Irl
Italy in l9BB." The NeWTom or maxiscan was the first CBCT the process of composite veneered restorations. This system
system in the world, installed in 1996.13 later developed as a processing centre networked with satellite
digitizers around the world for the fabrication of all ceramic
frameworks.16'r7 Dr Mormann developed CEREC System, an
Dentistry in 21st Century innovative approach to fabricate same day restorations at the
chair side in the dental office.r8
With the induction of 3D printing in dentistry particu-
Application of 3D technology and larly in the streams of oral and maxillofacial surgery and or-
CAD-CAM thodontics, future dentists and patients are now looking at
Frangois Duret, in the 1970s, conceptualised and adapted quality control in rehabilitation, and customised lingual and
the use of digital technology used in industry to dentistry. labial appliances. 3D printing has numerous applications in
The most significant and useful application was digital im- dentistry although the full potential of this technology is yet
pression making either directly in the mouth or indirectly to be explored.'e'20
on a model. These clinical applications were the outcomes
of research as a part of his thesis exercise having the title The
optical imprint'.
The 3D scan of impressions is transferred to production
Key Points
I
'fhe art and science of dental practice has evolved
milling machines through a process of computer-assisted since
manufacturing (CAM) to create dental restorations such as in- ancient Egyptians times to modern era of high speed,
lays and crowns. First dental CAD-CAM was invented in Zurich precision and lately digitalisation. The science of den-
by Siemens and sold by SIRONA.1a.r5 Dr Anderson developed tistry has contributions from the fields of medicine, engi-
Procera System. He attempted to fabricate titanium copings neering, computer sciences, material sciences and many
by spark erosion and introduced CAD-CAM technology into more.

. References
L

References for this chapter are found on the companion website wwwmedenact.com.

Suggested reading
Weinberger BW. Historical rdsumd of the evolution and groMh of orthodonti
a. I Am Dent Assoc 1934;21:2OOl_21. Cited
from wahl N. orthodontics in 3 milrennia. chapter 16. Late 2'th-century
fixed applianc es. Am I orthod Dentofaciar orthop
2008; r34(6): 827 -30. PMID: 19061 811.
il. Dewel BF Editorial: orrhodontosie, orrhodontics, or dentofacial orthopedics.
Am I orthod r9z6;zo(3):32g. pubMed pMID:
1066971.
III. Mozzo P' Procacci c, Tacconi A, Martini Pr, Andreis IA. A new volumetric
cr machine for dental imaging based on the cone
beam technique: preliminary results. Eur Radiol rgg8;8(9):1558-64. pubMed pMID:
9866261.

8
 Chapter 1.2

H istory of orthodontics

CHAPTER OUTTINE

Orthodontics in ancient times Orthodontics during 1960-70

Orthodontics in 17-18th century and European Contributions of Charles H. Tweed
dominance 9 (June 1 895-January 1 970) 21
Pierre Fauchard father of modern dentistry Orthodontics during'1970-80: pre-adjusted
and first fixed appliance 9 appliances 22
Contributions of Joachim Lefoulon 10 Evolution of pre-adjusted appliances and bonding:
American dentistry and orthodontics hallmark of contemporary orthodontics 22
in mid-19th century 10 Orthodontics during 1980-90: clinical success with
Contribution of Edward Hanley Angle to the twin block popularised functional
orthodontic profession (1 855-1 930) 11 appliance
Edward Angle's inventions and teachings 14 Temporary anchorage devices: major game
changer in orthodontic practice
The first three decades of 20th century, 1900-30:
beginning of biological foundation of orthodontics 15 Auto-transplantation of teeth in the management
of space 24
Orthodontics during 1930-40: Functional appliance
and cephalometrics 't8 Orthodontics during 2000-1 8 24
Orthodontics during'l 940-50: Tweed's Robotic orthodontics 24
concepts of growth 19 Orthodontics beyond 2020 24
Orthodontics during 1950-60: emphasis Key Points 25
on cephalometrics 20

Galen (129-199), suggested treatment of irregular teeth by

Orthodontics in ancient times filing of the teeth to gain space. It was Fabricius (1619) who
suggested extraction of teeth in
case of crowding.t Follow-
In Ancient times, irregular teeth have been located in the ing years saw some evolutionin dental profession in France
skulls of Neanderthal man who existed about 50,000 BC. An- where dental surgeons could undergo formal training and
cient Creeks and Etruscan artefacts exhibit designed devices/ practice correction of dental irregularities.
appliances to exert pressure on teeth. Archaeologists have dis-
covered Egyptian mummies with crude metal bands wrapped
around individual teeth. It is speculated that catgut was used Orthodontics in 17-18th century and
to close the gapsl (Fig. 1.1.1B).
European dominance
Hippocrates era, 400 BC to 16th century. Ancient Greek l

physicians mentioned dental irregularities as early as 400 BC.

Celsus (in Rome, 25 BC-50 AD) advised the removal of de-
Pierre Fauchard, father of modern dentistry
ciduous teeth once the permanent teeth have erupted and treat- and first fixed appliance
ment of crooked or irregular teeth could be attempted by pres- Pierre Fauchard (1678-March 22, 1767), a French physician is
sure exerted by the finger. He stated, 'lf a second tooth should known as 'father of modem dentistry' for his innumerable scien-
happen to grow in children before the first has fallen out, that tific contributions. He is also known for the first description of
ought to be shed is to be drawn our, and the new one daily 'brace'the'bandeau', the forerunner of Angle's E Arch appliance
pushed toward its place by means of the finger until it arrives (Fig. 1 . 1 .2 A, B). The bandeau was made of gold. Ir was used as
at its iust proportionl' In all probability, Pliny the Elder was a firm arch to which irregular teeth were tied using waxed linen
the first to use (AD 23-79), mechanical rreatment, which was or silk threads. He discovered that the teeth position could be
filing elongated teeth to bring them into proper alignment.l corrected, as the teeth would follow the pattem of the brace.
9
 Section lrl Historical aspects of orthodontics: ancient, yesteryears, yesterdays, today and tomorrow

Dr Fauchard, The Surgeon Dentist, is also known for writ- First plaster models. In 1836, Friedrich Christoph Kneisel,
ing the first complete scientific description of dentistry 'Le a German dentist, was first to use plaster models to record
Chirurgien Dentiste', published as early as 1728. Dr Fau- malocclusion. He used chin straps for correction of prognath-
chard who worked in Royal French Nary, ioining, Alexander ic mandible and hence, became the first to use a removable
Poteleret, at the age of 15, was greatly influenced by surgeon appliance. Kneisel (1797-1887) also wrote the 2l-page'Der
maior, Alexander Poteleret, and got interested in diseases of Schiefstand der Ziihne, dessen Ursachen und Abhilfe einer neuen,
the mouth, which caused much suffering in sailors on long sicheren und schmerzlosen H eilmethode' lD ental malposition-
voyages. Dr Fauchard studied medicine and later practised at ing, its causes and remedies using a novel, safe and painless
Angers University Hospital. He moved to Paris in 1723, at the method]. The first regulatory plate was made by Christopher
age of 45 years, where he completed the first 600-page manu- Starr Brewster in 1840; it was made of caoutchouc.
script. Next 5 years were spent on modifting and updating
the text based on feedback from his peers; by the time it was Contributions of Joachim Lefoulon
published in 17 28 in two volumes, it swelled to 783 pages.'
'Le Chirurgien Dentiste' is considered to be the first major The year 1841 is perhaps one of the historic years in the den-
description of dentistry. It described the basic oral anatomy, tal profession, when Joachim Lefoulon, in his book Nouueau
and function, signs and symptoms of oral pathology, op- traite de I'art du dentiste, used the term Orthodontosie, which
erative methods for removing tooth decay and restorations, the Americans simplified to 'orthodontia' and, later, to 'or-
periodontal disease, orthodontics, replacement of missing thodonticsln
teeth, and tooth transplantation. Dr Fauchard described a An elastic gold archwire was ried on the palatal side to treat
labial arch made of ivory for use in orthodontics.2 dental crowding. The wire has dual effect on relief of dental
The second edition was published in 1746, and the third crowding and also a moulding shaping effect on the alveolar
one in 1786. In 1733, the book was translated into German process, it can be said that this appliance was the first step
language. towards'orthodontics'.'
Dr Fauchard collected examples of treatment of inegular Lefoulon, suggested malocclusion can be caused by these
teeth to describe them particularly well, concerning the erup- factors:
tion of teeth, he wrote: '... teeth empt sooner or latet depend- (1) Constitutional differences brought about by social,
ing on the children's forces', with their'temperament'being
economic, and geographic conditions
possibly so big as to present with teeth already at the time
(2) Prenatal conditions
of birth. He described, among other things: a rddressement (3) A disease process, such as scrofula and
force using a'pelican', where the tooth was moved within the
(4) Abnormal pressures during the speech.
socket. He then ligated the tooth to its neighbours until heal-
ing took place. At that time, most attention was paid only to The first molar band was fixed with a screw in 1g4l by I. U.
the alignment of teeth almosr exclusively in the maxilla. He Afexis Schang€. His book Prdcis sur le Redressement des Dents
also suggested interproximal polishing and splinting of the described an adaptable band clamp rhat was fixed to the tooth
tooth with a follow-up trearmenr bringing about the desired using a screw. He was also the first to mention a need for a
result within a week.t,' period of retention after the treatment.
During these years (1222-66), phillip pfaff, a surgeon den_ The first classification of malocclusion. Georg Carabelli
tist, for the first time described taking the impression with in 1842 presented first ever classification of malocclusion. He
sealing wax. However, he denied that milk teeth have roots, presented a novel classification ofvarious types ofocclusion,
which was later contradicted by Iohn Hunter (1728_93), a which was highly regarded in the German-speaking world for
British surgeon, inspector-general of hospitals, also worked in quite some time.
orthodontics and found our thar milk teeth do have roots. His William Henry Dwinelle (1819-96) was the firsr to use
observations included that, once they have erupted, they no screws and the first elastic rubber for orthodontics
in 1g46.
longer grow in width, but that crowding is the result of tooth The first report on bone remodelling (1g59). Iohn Tomes
movement. He determined that milk molars are bigger than was the first to show remodelling processes in the alveolar
premolars, but front milk teeth are smaller than permanent bone with bone resorption in the direction pressure is exerted,
teeth.2 and bone apposition on the side of relief.,
fohn Hunter (1728-93) was first to investigate the growth
in animals, using pigs' mandibles. A metal ring that was in_
serted at the front edge of the ascending mandibular ramus American dentistry and orthodontics in
in growing animals that moved to the centre due to the op_
position ar the front edge and resorption at the hind edge of
the mandible. In the United States before the 1g30s, there was no formal
The inclined plane. John Hunter was first to use an inclined professional education or a dental degree. The physicians,
plane made of silver in the anterior tooth_bearing area of the barbers, or charlatans performed the woik and procedures in
jaws to treat prognathia and a metal arch with
ligatures. Adam mouth. The literature has little contributions from American
Anton Brunner was first to use an inclined plane in l77l. authors related to orthodontics until 1Bg0r and the term Mal,
However, it was L. I. Catalan who propagated an inclined occlusion was not known.
plane around 180B as its construction. The inclined plane
is During mid-19th century significant developments took
now named after him. place which contributed to evolving a dental profession
with
10
l History of orthodontics
@112r I
formal education and uaining. In 1839, the American Joumal of
Dentnl Science, the world's first dental joumal, had begun pub-
lication and a year later, the world's first dental school, the Bal-
timore College of Dental Surgery was founded. The first formal
dental degree, DDS degree was awarded from Baltimore. ffi
ll ,,
It is at Baltimore College of Surgery that the first lectures on
'irregularities' of the teeth were given to undergraduates by
Chapin Harris. Norman Kingsley, who is considered'Father of
Orthodontia in the USA, lectured students on the causes and
correction of malocclusion ( 1 872).
Before 1910, orthodontics was taught as a branch of pros-
thetics, the techniques for correction of irregular teeth with
little or no emphasis on science.
Norman William Kingsley, 1866. Dr Kingsley suggested
prosthetic treatment of cleft lip and palate and introduced
Figure 1.2.2 Dr George B. Crozat (1893-1956) developed a univer-
extraoral traction device. His student, Walter Harris Coffin,
sal wire device. which is more popularly known as Crozat appli-
in 1B8l (Fig. t.2.t), found an innovative method for regula- ance and Crozat retainer. Source: Wahl N. Orthodontics in 3 millennia.
tion of irregular teeth using a bent W spring made of piano Chapter 5: the American Board of Orthodontics, Albert Ketcham, and
wire embedded on both sides into l.ulcanite, later replaced by early 20th-century apphances. Am J Orthod Dentofacial Orthop 2005
acrylic. The spring is free to expand in the middle and thereby Oct;128(4):53540.
used as expansion appliance to move two sides of the alveolar
process in the maxilla. this science indebted. His life has been spent nursing and de-
fohn Nutting Farrar (1839-1913). Dr Farrar authored text veloping it',
on orthodontics 'lnegularities of the Teeth and TheirTreatment' Cited from A Biographical Portrait of Edward Hartley An-
first in 1888, which went through six editions; and more rhan gle, the First Specialist in Orthodonrics', written by Peck S.6 in
90 articles on gingival pathologies and irregularities of the teeth. a three part series and the Editorial for the first issue of The
Fanar opined that forces for moving the teeth should not be International Journal of Orthodontia in 1915 by Martin Dewey,
continuous and suggested the theory of intermittent force. He DDS, MD, one of his most accomplished students, the follow-
developed a screw to deliver this kind of force in controlled in- ing write-up gives a brief record of E. H. Angle.
crements by activating the device 'about7l24O inch every mom- "No personality central to the history of orthodontics stim-
ing and the same in the evening'. ulated as much progress, excitement, and polarity as Edward
Around the same years Dr George B. Crozat (1S93-1966) Hartley Angle, MD, DDS (1855-1930), the acknowledged
developed a universal wire device, which is more popularly founder of this clinical speciality. Early in the 20th century
known as Crozat appliance and Crozat retainer (Fig. 1.2.2; he dominated the emergence of 'orthodontia as a science and
Box 1.2.1A, B, C). a specialityi This inventive doctor gave malocclusion the pri-
macy and order it needed."
Edward Hartley Angle spent his boyhood on his parents'
farm in District, 'Ballibay', Herrick Township, Bradford Coun-
Contribution of Edward Hartley Angle to ty, Pennsylvania. His mother Isabel, in the year 1874, intro-
the orthodontic profession (1855-1930)5-8 duced HART (Angle's nickname) at age lB years to a nearby
dentist to learn dentistry as an office apprentice. Later, Angle
'lt is well known that Dr Edward H. Angle is the nestor of enrolled himself at College of Dental Surgery in Philadel-
orthodontia. To him, more than to any other individual is phia for the DDS programme. The DDS programme was then
arranged in two 6-month terms spaced over a nominal two
years.
In 1878, Edward Angle initiated his profession by setting
up a general practice of dentistry in the centre of town at
Bradford County seat, Towanda. In 1881, his health dete-
riorated, and he decided to abandon dentistry on his phy-
sician's advice to live in an outdoor environment. Angle
moved to live in Minneapolis, Minnesota where his health
improved. While Angle was contemplating to abandon den-
tistry to avoid physically demanding dental profession, he
set up a lucrative sheep-raising business in Montana with his
friends and brother. Unfortunately, a record-breaking deep
freeze that year killed off the entire herd and he lost all his
savings.
Figure 1.2.1 The W spring made of piano wire by Walter Harris Cof- By mid-1882, he moved back to practice again. His curiosi-
fin (1881). Source: Wahl N. Orthodontics in 3 millennia. Chapter 2:entering ty, attention and indulgence in 'regulating'the'irregular teeth'
the modern era. Am J Orthod Dentofacial Ofthop 2005 Apr,127(4):51A5. continued to flourish. The breaking point in his career was his

11
Section I f i Historical aspects of orthodontics: ancient, yesteryears, yesterdays, today and tomorrow

Box 1 .2.1A Origin and worldwide contributions in orthodontics from 400 BC to 19th tentury

Years Events

400 Bc Hippocrates era: Dental irregularities mentioned the first time

25 BC-50 AD Celsus recommended the removal of milk teeth once the permanent teeth have erupted, and the straightening of crooked or
irregular teeth by pressure exerted with the finger
129-199 Galen suggested treatment of the irregular teeth by filing of the teeth to gain space
1 619 Fabricius suggested extraction of teeth in case of crowding
1678-1761 First description of 'brace' or the 'bandeau', the forerunner of Angleb E Arch appliance given by Pierre Fauchard. Bandeau was
used as a firm arch to which inegular teeth were tied using waxed linen or silk threads
1722-1766 Phillip Pfaff, a surgeon dentist, forthe firsttime described taking the impression with sealing wax
1728-1793 John Hunter, a British surgeon, inspector-general of hosprtals, also worked in orthodontics and found out that milk teeth do
have roots. He was also the first to investigate growth of mandible in animals
Adam Anton Brunner was the first to use an inclined plane in 1 771 . However, it was L. J. Catalan who propagated an inclined
plane around 1808 as his own construction
1 836 Friedrich Christoph Kneisel, a German dentist, was first to use plaster models to record malocclusion. He used chin straps for
correction of prognathic mandible and hence, became the first to use a removable appliance
Joachim Lefoulon, in his book Nouveau traite de l'aft du dentiste, used the term 'Orthodontia'. He used an elastic qold archwire
on the palatal side to treat crowding
M. Alexis Schang6 described an adaptable band clamp that was fixed to the tooth using a screw; he was probably the first to
realise that treatment should be followed by a period of retention
1842 Georg Carabelli presented a novel classificatron of types of occlusion
1846 Claude Lachaise and Elisha Gustavus Tucker were the first to use the elasticity of rubber straps for orthodontic purposes
1 859 John Tomes was the first to show remodelling processes in the alveolar bone
1872 Norman Kingsley, considered as the 'Father of orthodontia in USA, lectured students on the causes and correction of
malocclusion at Baltimore College of Dental 5urgery
1 878-1 930 Edward H. Angle's contributions are listed in Box 1.2.2
'1881
Walter Harris Coffin found an innovative method for regulation of irregular teeth using a bent W spring made of piano wire
embedded on both sides into vulcanite, later replaced by acrylic
1 888 John Nutting Farrar wrote on irregularities of the teeth and their treatment
1 890 Intermaxillary elastics proposed by Dr Case and Dr Baker However it became popular as Baker's Anchoraoe

Box 1 2.1 B origin and worldwide contributions in orthodontics, 20th century

Events

George B Crozat developed a universal wrre device, which is more popularly known
as Crozat appliance and Crozat retainer
charles A Hawley published 'Determination of Normal Arch and rts Application
to orthodontia, and introduced the retainer
appliance that bears his name: Hawleys appliance
191 1 Albin oppenheim, an Austrian-Hungarian born physician turned orthodontist, was
the first to report tissue changes more so in
bone during orthodontic tooth movement. His flrsi article on this subject *ui'prlilin"o
in Vienna
Albert H Ketcham. one of the first to introduce the roentgenogram and photography
into orthodontic practice
fhe lnternational lournal of Orthodontia and Oral Surge4l was started in 19i 5
John v Mershon introduced the removable lingual arch based on the principle
that teeth must be free and unrestricted for
adaptatton to normal growth
19'18 Alfred Rogers introduced the concept of myofunctional tnerapy
1921 Dr case published his maiorwork, 'A Practical Treatise on the Techniques
and principle of Dental orthopedia and prosthetic
Correction of the Cleft palate,
1924 concept of orientation of face beyond teeth was introduced. paul
simon,s Gnathostatics
1931
orthodontia'rhrs pioneerins technique tead to a new era or understandins
t1):IJi:?J:.',:[T:#,i;:J:i::.t'",.to or
Bolton s polnt: In recognition of Mrs chester c. Bolton
and her son charles B. Bolton who funded manufacture of
cephalostat head holder and x-ray apparatus, which was installed first
at anatomical taboratory of the western Reserve university
1 933 Dr' Andressen revrved Monoblock appliance first
developed by Piene Robin in 1902 to new appliance called
Dr Robert E Moyers and sam Pruzansky inducted electromyography Activaror.
to study the effect of musculature on occlusion
Biorks study on normal variations and mechanism of prognathrsm
as well as relationship between facial build and
representative materral the bite in
Another Random Scribd Document
with Unrelated Content
 The action of hydrogen peroxide on a solution of
chromic acid or of potassium dichromate gives a blue
solution, which very quickly becomes colourless with
the disengagement of oxygen. Barreswill showed
that this is due to the formation of a perchromic
anhydride, Cr2O7, corresponding with sulphur
peroxide. This peroxide is remarkable from the fact
that it very easily dissolves in ether and is much
more stable in this solution, so that, by shaking up
hydrogen peroxide mixed with a small quantity of
chromic acid, with ether, it is possible to transfer all
the blue substance formed to the ether.[6 bis]
With oxygen acids, chromic acid evolves oxygen;
for example, with sulphuric acid the following
reaction takes place: 2CrO3 + 3H2SO4 = Cr2(SO4)3 +
O3 + 3H2O. It will be readily understood from this
that a mixture of chromic acid or of its salts with
sulphuric acid forms an excellent oxidising agent,
which is frequently employed in chemical laboratories
and even for technical purposes as a means of
oxidation. Thus hydrogen sulphide and sulphurous
anhydride are converted into sulphuric acid by this
means. Chromic acid is able to act as a powerful
oxidising agent because it passes into chromic oxide,
and in so doing disengages half of the oxygen
contained in it: 2CrO3 = Cr2O3 + O3. Thus chromic
anhydride itself is a powerful oxidising agent, and is
therefore employed instead of nitric acid in galvanic
batteries (as a depolariser), the hydrogen evolved at
the carbon being then oxidised, and the chromic acid
converted into a non-volatile product of deoxidation,
instead of yielding, as nitric acid does, volatile lower
oxides of offensive odour. Organic substances are
more or less perfectly oxidised by means of chromic
anhydride, although this generally requires the aid of
heat, and does not proceed in the presence of
alkalis, but generally in the presence of acids. In
acting on a solution of potassium iodide, chromic
acid, like many oxidising agents, liberates iodine; the
reaction proceeds in proportion to the amount of
CrO3 present, and may serve for determining the
amount of CrO3, since the amount of iodine liberated
can be accurately determined by the iodometric
method (Chapter XX., Note 42). If chromic anhydride
be ignited in a stream of ammonia, it gives chromic
oxide, water, and nitrogen. In all cases when chromic
acid acts as an oxidising agent in the presence of
acids and under the action of heat, the product of its
deoxidation is a chromic salt, CrX3, which is
characterised by the green colour of its solution, so
that the red or yellow solution of a salt of chromic
acid is then transformed into a green solution of a
chromic salt, derived from chromic oxide, Cr2O3,
which is closely analogous to Al2O3, Fe2O3, and other
bases of the composition R2O3. This analogy is seen
in the insolubility of the anhydrous oxide, in the
gelatinous form of the colloidal hydrate, in the
formation of alums,[7] of a volatile chloride of
chromium, &c.[7 bis]
Chromic oxide, Cr2O3, rarely found, and in small
quantities, in chrome ochre, is formed by the
oxidation of chromium and its lower oxides, by the
reduction of chromates (for example, of ammonium
or mercuric chromate) and by the decomposition
(splitting up) of the saline compounds of the oxide
itself, CrX3 or Cr2X6, like alumina, which it resembles
in forming a feeble base easily giving double and
basic salts, which are either green or violet.
The reduction of chromic oxide—for instance, in a
solution by zinc and sulphuric acid—leads to the
formation of chromous oxide, CrO, and its salts, CrX2,
of a blue colour (see Notes 7 and 7bis). The further
reduction[8] of oxide of chromium and its
corresponding compounds gives metallic chromium.
Deville obtained it (probably containing carbon) by
reducing chromic oxide with carbon, at a
temperature near the melting point of platinum,
about 1750°, but the metal itself does not fuse at
this temperature. Chromium has a steel-grey colour
and is very hard (sp. gr. 5·9), takes a good polish,
and dissolves in hydrochloric acid, but cold dilute
sulphuric and nitric acids have no action upon it.
Bunsen obtained metallic chromium by decomposing
a solution of chromic chloride, Cr2Cl6, by a galvanic
current, as scales of a grey colour (sp. gr. 7·3).
Wöhler obtained crystalline chromium by igniting a
mixture of the anhydrous chromic chloride Cr2Cl6
(see Note 7 bis) with finely-divided zinc, and sodium
and potassium chlorides, at the boiling-point of zinc.
When the resultant mass has cooled the zinc may be
dissolved in dilute nitric acid, and grey crystalline
chromium (sp. gr. 6·81) is left behind. Frémy also
prepared crystalline chromium by the action of the
vapour of sodium on anhydrous chromic chloride in a
stream of hydrogen, using the apparatus shown in
the accompanying drawing, and placing the sodium
and the chromic chloride in separate porcelain boats.
The tube containing these boats is only heated when
it is quite full of dry hydrogen. The crystals of
metallic chromium obtained in the tube are grey
cubes having a considerable hardness and
withstanding the action of powerful acids, and even
of aqua regia. The chromium obtained by Wöhler by
the action of a galvanic current is, on the contrary,
acted on under these conditions. The reason of this
difference must be looked for in the presence of
impurities, and in the crystalline structure. But in any
case, among the properties of metallic chromium,
the following may be considered established: it is
white in colour, with a specific gravity of about 6·7, is
extremely hard in a crystalline form, is not oxidised
by air at the ordinary temperature, and with carbon
it forms alloys like cast iron and steel.
 Fig. 92.—Apparatus for the preparation of
metallic chromium by igniting chromic
chloride and sodium in a stream of hydrogen.
The two analogues of chromium, molybdenum and
tungsten (or wolfram), are of still rarer occurrence in
nature, and form acid oxides, RO3, which are still less
energetic than CrO3. Tungsten occurs in the
somewhat rare minerals, scheelite, CaWO4, and
wolfram; the latter being an isomorphous mixture of
the normal tungstates of iron and manganese,
(MnFe)WO4. Molybdenum is most frequently met
with as molybdenite, MoS2, which presents a certain
resemblance to graphite in its physical properties and
softness. It also occurs, but much more rarely, as a
yellow lead ore, PbMoO4. In both these forms
molybdenum occurs in the primary rocks, in granites,
gneiss, &c., and in iron and copper ores in Saxony,
Sweden, and Finland. Tungsten ores are sometimes
met with in considerable masses in the primary rocks
of Bohemia and Saxony, and also in England,
America, and the Urals. The preliminary treatment of
the ore is very simple; for example, the sulphide,
MoS2, is roasted, and thus converted into sulphurous
anhydride and molybdic anhydride, MoO3, which is
then dissolved in alkalis, generally in ammonia. The
ammonium molybdate is then treated with acids,
when the sparingly soluble molybdic acid is
precipitated. Wolfram is treated in a different
manner. Most frequently the finely-ground ore is
repeatedly boiled with hydrochloric and nitric acids,
and the resultant solutions (of salts of manganese
and iron) poured off, until the dark brown mass of
ore disappears, whilst the tungstic acid remains,
mixed with silica, as an insoluble residue; it is treated
also with ammonia, and is thus converted into
soluble ammonium tungstate, which passes into
solution and yields tungstic acid when treated with
acids. This hydrate is then ignited, and leaves
tungstic anhydride. The general character of
molybdic and tungstic anhydrides is analogous to
that of chromic anhydride; they are anhydrides of a
feebly acid character, which easily give polyacid salts
and colloid solutions.[8 bis]
Hydrogen (which does not directly form
compounds with Cr, Mo, and W) reduces molybdic
and tungstic anhydride at a red heat; and this forms
the means of obtaining metallic molybdenum and
tungsten. Both metals are infusible, and both under
the action of heat form compounds with carbon and
iron (the addition of tungsten to steel renders the
latter ductile and hard).[9] Molybdenum forms a grey
powder, which scarcely aggregates under a most
powerful heat, and has a specific gravity of 8·5. It is
not acted on by the air at the ordinary temperature,
but when ignited it is first converted into a brown,
and then into a blue oxide, and lastly into molybdic
anhydride. Acids do not act on it—that is, it does not
liberate hydrogen from them, not even from
hydrochloric acid—but strong sulphuric acid
disengages sulphurous anhydride, forming a brown
mass, containing a lower oxide of molybdenum.
Alkalis in solution do not act on molybdenum, but
when fused with it hydrogen is given off, which
shows, as does its whole character, the acid
properties of the metal. The properties of tungsten
are almost identical; it is infusible, has an iron-grey
colour, is exceedingly hard, so that it even scratches
glass. Its specific gravity is 19·1 (according to
Roscoe), so that, like uranium, platinum, &c., it is
one of the heaviest metals.[9 bis] Just as sulphur and
chromium have their corresponding persulphuric and
perchromic acids, H2S2O8 and H2CrO8, having the
properties of peroxides, and corresponding to
peroxide of hydrogen, so also molybdenum and
tungsten are known to give permolybdic and
pertungstic acids, H2Mo2O8 and H2W2O8, which have
the properties of true peroxides, i.e. easily disengage
iodine from KI and chlorine from HCl, easily part with
their oxygen, and are formed by the action of
peroxide of hydrogen, into which they are readily
reconverted (hence they may be regarded as
compounds of H2O2 with 2MoO3 and 2WO3), &c.
Their formation (Boerwald 1884, Kemmerer 1891) is
at once seen in the coloration (not destroyed by
boiling), which is obtained on mixing a solution of
the salts with peroxide of hydrogen, and on treating,
for instance, molybdic acid with a solution of
peroxide of hydrogen (Péchard 1892). The acid then
forms an orange-coloured solution, which after
evaporation in vacuo leaves Mo2H2O84H2O as a
crystalline powder, and loses 4H2O at 100°, beyond
which it decomposes with the evolution of oxygen.[9
tri]
 Uranium, U = 240, has the highest atomic weight
of all the analogues of chromium, and indeed of all
the elements yet known. Its highest salt-forming
oxide, UO3, shows very feeble acid properties.
Although it gives sparingly-soluble yellow compounds
with alkalis, which fully correspond with the
dichromates—for example, Na2U2O7 = Na2O,2UO3,[10]
—yet it more frequently and easily reacts with acids,
HX, forming fluorescent yellowish-green salts of the
composition UO2X2, and in this respect uranic
trioxide, UO3, differs from chromic anhydride, CrO3,
although the latter is able to give the oxychloride,
CrO2Cl2. In molybdenum and tungsten, however, we
see a clear transition from chromium to uranium.
Thus, for example, chromyl chloride, CrO2Cl2, is a
brown liquid which volatilises without change, and is
completely decomposed by water; molybdenum
oxychloride, MoO2Cl2, is a crystalline substance of a
yellow colour, which is volatile and soluble in water
(Blomstrand), like many salts. Tungsten oxychloride,
WO2Cl2, stands still nearer to uranyl chloride in its
properties; it forms yellow scales on which water and
alkalis act, as they do on many salts (zinc chloride,
ferric chloride, aluminium chloride, stannic chloride,
&c.), and perfectly corresponds with the difficultly
volatile salt, UO2Cl2 (obtained by Peligot by the
action of chlorine on ignited uranium dioxide, UO2),
which is also yellow and gives a yellow solution with
water, like all the salts UO2X2. The property of uranic
oxide, UO3, of forming salts UO2X2 is shown in the
fact that the hydrated oxide of uranium, UO2(HO)2,
which is obtained from the nitrate, carbonate, and
other salts by the loss of the elements of the acid, is
easily soluble in acids, as well as in the fact that the
lower grades of oxidation of uranium are able, when
treated with nitric acid, to form an easily
crystallisable uranyl nitrate, UO2(NO3)2,6H2O; this is
the most commonly occurring uranium salt.[11]
Uranium, which gives an oxide, UO3, and the
corresponding salt UO2X2 and dioxide UO2, to which
the salts UX4 correspond, is rarely met with in
nature. Uranite or the double orthophosphate of
uranic oxide, R(UO2)H2P2O8,7H2O, where R = Cu or
Ca, uranium-vitriol U(SO4)2,H2O, samarakite, and
æschynite, are very rarely found, and then only in
small quantities. Of more frequent and abundant
occurrence is the non-crystalline, earthy brown
uranium ore known as pitchblende (sp. gr. 7·2),
which is mainly composed of the intermediate oxide,
U3O8 = UO2,2UO3. This ore is found at Joachimsthal
in Bohemia and in Cornwall. It usually contains a
number of different impurities, chiefly sulphides and
arsenides of lead and iron, as well as lime and silica
compounds. In order to expel the arsenic and
sulphur it is roasted, ground, washed with dilute
hydrochloric acid, which does not dissolve the
uranoso-uranic oxide, U3O8, and the residue is
dissolved in nitric acid, which transforms the uranium
oxide into the nitrate, UO2(NO3)2.
It must be observed that the oxide of uranium,
first distinguished by Klaproth (1789), was for a long
time regarded as able to give metallic uranium under
the action of charcoal and other reducing agents
(with the aid of heat). But the substance thus
obtained was only the uranium dioxide, UO2. The
compound nature of this dioxide,[12] or the presence
of oxygen in it, was demonstrated by Peligot (1841),
by igniting it with charcoal in a stream of chlorine.
He thus obtained a volatile uranium tetrachloride,
UCl4,[13] which, when heated with sodium, gave
metallic uranium as a grey metal, having a specific
gravity of 18·7, and liberating hydrogen from acids,
with the formation of green uranous salts, UX4,
which act as powerful reducing agents.[14]
As the salts of uranic oxide are reduced in the
absence of organic matter by the action of light, and
as they impart a characteristic coloration to glass,[15]
they find a certain application in photography and
glass work.
If we compare together the highly acid elements,
sulphur, selenium, and tellurium, of the uneven
series, with chromium, molybdenum, tungsten, and
uranium of the even series, we find that the
resemblance of the properties of the higher form RO3
does not extend to the lower forms, and even
entirely disappears in the elements, for there is not
the smallest resemblance between sulphur and
chromium and their analogues in a free state. In
other words, this means that the small periods, like
Na, Mg, Al, Si, P, S, Cl, containing seven elements, do
not contain any near analogues of chromium,
molybdenum, &c., and therefore their true position
among the other elements must be looked for only in
those large periods which contain two small periods,
and whose type is seen in the period containing: K,
Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As,
Se, Br. These large periods contain Ca and Zn, giving
RO, Sc, and Ga of the third group, Ti and Ge giving
RO2, V and As forming R2O5, Cr and Se of the sixth
group, Mn and Br of the seventh group, and the
remaining elements, Fe, Co, Ni, form connective
members of the intermediate eighth group, to the
description of the representatives of which we shall
turn in the following chapters. We will now proceed
to describe manganese, Mn = 55, as an element of
the seventh group of the even series, directly
following after Cr = 52, which corresponds with Br =
80 to the same degree that Cr does with Se = 79.
For chromium, selenium, and bromine very close
analogues are known, but for manganese as yet
none have been obtained—that is, it is the only
representative of the even series in the seventh
group. In placing manganese with the halogens in
one group, the periodic system of the elements only
requires that it should bear an analogy to the
halogens in the higher type of oxidation—i.e. in the
salts and acids—whilst it requires that as great a
difference should be expected in the lower types and
elements as there exists between chromium or
molybdenum and sulphur or selenium. And this is
actually the case. The elements of the seventh group
form a higher salt-forming oxide, R2O7, and its
corresponding hydrate, HRO4, and salts—for
example, KClO4. Manganese in the form of potassium
permanganate, KMnO4, actually presents a great
analogy in many respects to potassium perchlorate,
KClO4. The analogy of the crystalline form of both
salts was shown by Mitscherlich. The salts of
permanganic acid are also nearly all soluble in water,
like those of perchloric acid, and if the silver salt of
the latter, AgClO4, be sparingly soluble in water, so
also is silver permanganate, AgMnO4. The specific
volume of potassium perchlorate is equal to 55,
because its specific gravity = 2·54; the specific
volume of potassium permanganate is equal to 58,
because its specific gravity = 2·71. So that the
volumes of equivalent quantities are in this instance
approximately the same whilst the atomic volumes of
chlorine (35·5/1·3 = 27) and manganese (55/7·5)
are in the ratio 4 : 1. In a free state the higher acids
HClO4 and HMnO4 are both soluble in water and
volatile, both are powerful oxidisers—in a word, their
analogy is still closer than that of chromic and
sulphuric acids, and those points of distinction which
they present also appear among the nearest
analogues—for example, in sulphuric and telluric
acids, in hydrochloric and hydriodic acids, &c.
Besides Mn2O7 manganese gives a lower grade of
oxidation, MnO3, analogous to sulphuric and chromic
trioxides, and with it corresponds potassium
manganate, K2MnO4, isomorphous with potassium
sulphate.[16] In the still lower grades of oxidation,
Mn2O3 and MnO, there is hardly any similarity to
chlorine, whilst every point of resemblance
disappears when we come to the elements
themselves—i.e. to manganese and chlorine—for
manganese is a metal, like iron, which combines
directly with chlorine to form a saline compound,
MnCl2, analogous to magnesium chloride.[17]
Manganese belongs to the number of metals
widely distributed in nature, especially in those
localities where iron occurs, whose ores frequently
contain compounds of manganous oxide, MnO, which
presents a resemblance to ferrous oxide, FeO, and to
magnesia. In many minerals magnesia and the
oxides allied to it are replaced by manganous oxide;
calcspars and magnesites—i.e. R″CO3 in general—are
frequently met with containing manganous
carbonate, which also occurs in a separate state,
although but rarely. The soil also and the ash of
plants generally contain a small quantity of
manganese. In the analysis of minerals it is generally
found that manganese occurs together with
magnesia, because, like it, manganous oxide remains
in solution in the presence of ammoniacal salts, not
being precipitated by reagents. The property of this
manganous oxide, MnO, of passing into the higher
grades of oxidation under the influence of heat,
alkalis, and air, gives an easy means not only of
discovering the presence of manganese in admixture
with magnesia, but also of separating these two
analogous bases. Magnesia is not able to give higher
grades of oxidation, whilst manganese gives them
with great facility. Thus, for instance, an alkaline
solution of sodium hypochlorite produces a
precipitate of manganese dioxide in a solution of a
manganous salt: MnCl2 + NaClO + 2NaHO = MnO2 +
H2O + 3NaCl; whilst magnesia is not changed under
these circumstances, and remains in the form of
MgCl2. If the magnesia be precipitated owing to the
presence of alkali, it may be dissolved in acetic acid,
in which manganese dioxide is insoluble. The
presence of small quantities of manganese may also
be recognised by the green coloration which alkalis
acquire when heated with manganese compounds in
the air. This green coloration depends on the
property of manganese of giving a green alkaline
manganate: MnCl2 + 4KHO + O2 = K2MnO4 + 2KCl +
2H2O. Thus the faculty of oxidising in the presence of
alkalis forms an essential character of manganese.
The higher grades of oxidation containing Mn2O7 and
MnO3 are quite unknown in nature, and even MnO2 is
not so widely spread in nature as the ores composed
of manganous compounds which are met with nearly
everywhere. The most important ore of manganese
is its dioxide, or so-called peroxide, MnO2, which is
known in mineralogy as pyrolusite. Manganese also
occurs as an oxide corresponding with magnetic iron
ore, MnO,Mn2O3 = Mn3O4, forming the mineral
known as hausmannite. The oxide Mn2O3 also occurs
in nature as the anhydrous mineral braunite, and in a
hydrated form, Mn2O3,H2O, called manganite. Both of
these often occur as an admixture in pyrolusite.
Besides which, manganese is met with in nature as a
rose-coloured mineral, rhodonite, or silicate, MnSiO3.
Very fine and rich deposits of manganese ores have
been found in the Caucasus, the Urals, and along the
Dnieper. Those at the Sharapansky district of the
Government of Kutais and at Nicopol on the Dnieper
are particularly rich. A large quantity of the ore (as
much as 100,000 tons yearly) is exported from these
localities.
Thus manganese gives oxides of the following
forms: MnO, manganous oxide, and manganous
salts, MnX2, corresponding with the base, which
resembles magnesia and ferrous oxide in many
respects; Mn2O3, a very feeble base, giving salts,
MnX3, analogous to the aluminium and ferric salts,
easily reduced to MnX2; MnO2, dioxide, generally
called peroxide, an almost indifferent oxide, or feebly
acid;[18] MnO3, manganic anhydride, which forms
salts resembling potassium sulphate;[18 bis] Mn2O7,
permanganic anhydride, giving salts analogous to the
perchlorates.
 All the oxides of manganese when heated with
acids give salts, MnX2, corresponding with the lower
grade of oxidation, manganous oxide, MnO.
Manganic oxide, Mn2O3, is a feebly energetic base; it
is true that it dissolves in hydrochloric acid and gives
a dark solution containing the salt MnCl3, but the
latter when heated evolves chlorine and gives a salt
corresponding with manganous oxide MnCl2—i.e. at
first: Mn2O3 + 6HCl = 3H2O + Mn2Cl6, and then the
Mn2Cl6 decomposes into 2MnCl2 + Cl2. None of the
remaining higher grades of oxidation have a basic
character, but act as oxidising agents in the presence
of acids, disengaging oxygen and passing into salts
of the lower grade of oxidation of manganese, MnO.
Owing to this circumstance, the manganous salts are
often obtained; they are, for instance, left in the
residue when the dioxide is used for the preparation
of oxygen and chlorine.[19]
As the salts of manganous oxide MnX2 closely
resemble (and are isomorphous with) the salts of
magnesia MgX2 in many respects (with the exception
of the fact that MnX2 are rose coloured and are easily
oxidised in the presence of alkalis), we will not dwell
upon them, but limit ourselves to illustrating the
chemical character of manganese by describing the
metal and its corresponding acids. The fact alone
that the oxides of manganese are not reduced to the
metal when ignited in hydrogen (whilst the oxides of
iron give metallic iron under these circumstances),
but only to manganous oxide, MnO, shows that
manganese has a considerable affinity for oxygen—
that is, it is difficult to reduce. This may be effected,
however, by means of charcoal or sodium at a very
high temperature. A mixture of one of the oxides of
manganese with charcoal or organic matter gives
fused metallic manganese under the powerful heat
developed by coke with an artificial draught. The
metal was obtained for the first time in this manner
by Gahn, after Pott, and more especially Scheele,
had in the last century shown the difference between
the compounds of iron and manganese (they were
previously regarded as being the same). Manganese
is prepared by mixing one of its oxides in a finely-
divided state with oil and soot; the resultant mass is
then first ignited in order to decompose the organic
matter, and afterwards strongly heated in a charcoal
crucible. The manganese thus obtained, however,
contains, as a rule, a considerable amount of silicon
and other impurities. Its specific gravity varies
between 7·2 and 8·0. It has a light grey colour, a
feebly metallic lustre, and although it is very hard it
can be scratched by a file. It rapidly oxidises in air,
being converted into a black oxide; water acts on it
with the evolution of hydrogen—this decomposition
proceeds very rapidly with boiling water, and if the
metal contain carbon.[20]
It has been shown above that if manganese
dioxide, or any lower oxide of manganese, be heated
with an alkali in the presence of air, the mixture
absorbs oxygen,[21] and forms an alkaline manganate
of a green colour: 2KHO + MnO2 + O = K2MnO4 +
H2O. Steam is disengaged during the ignition of the
mixture, and if this does not take place there is no
absorption of oxygen. The oxidation proceeds much
more rapidly if, before igniting in air, potassium
chlorate or nitre be added to the mixture, and this is
the method of preparing potassium manganate,
K2MnO4. The resultant mass dissolved in a small
quantity of water gives a dark green solution, which,
when evaporated under the receiver of an air-pump
over sulphuric acid, deposits green crystals of exactly
the same form as potassium sulphate—namely, six-
sided prisms and pyramids. The composition of the
product is not changed by being re-dissolved, if
perfectly pure water free from air and carbonic acid
be taken. But in the presence of even very feeble
acids the solution of this salt changes its colour and
becomes red, and deposits manganese dioxide. The
same decomposition takes place when the salt is
heated with water, but when diluted with a large
quantity of unboiled water manganese dioxide does
not separate, although the solution turns red. This
change of colour depends on the fact that potassium
manganate, K2MnO4, whose solution is green, is
transformed into potassium permanganate, KMnO4,
whose solution is of a red colour. The reaction
proceeding under the influence of acids and a large
quantity of water is expressed in the following
manner: 3K2MnO4 + 2H2O = 2KMnO4 + MnO2 +
4KHO. If there is a large proportion of acid and the
decomposition is aided by heat, the manganese
dioxide and potassium permanganate are also
decomposed, with formation of manganous salt.
Exactly the same decomposition as takes place under
the action of acids is also accomplished by
magnesium sulphate, which reacts in many cases like
an acid. When water holding atmospheric oxygen in
solution acts on a solution of potassium manganate,
the oxygen combines directly with the manganate
and forms potassium permanganate, without
precipitating manganese dioxide, 2K2MnO4 + O +
H2O = 2KMnO4 + 2KHO. Thus a solution of
potassium manganate undergoes a very
characteristic change in colour and passes from
green to red; hence this salt received the name of
chameleon mineral.[22]
 Potassium permanganate, KMnO4, crystallises in
well-formed, long red prisms with a bright green
metallic lustre. In the arts the potash is frequently
replaced by soda, and by other alkaline bases, but no
salt of permanganic acid crystallises so well as the
potassium salt, and therefore this salt is exclusively
used in chemical laboratories. One part of the
crystalline salt dissolves in 15 parts of water at the
ordinary temperature. The solution is of a very deep
red colour, which is so intense that it is still clearly
observable after being highly diluted with water. In a
solid state it is decomposed by heat, with evolution
of oxygen, a residue consisting of the lower oxides of
manganese and potassium oxide being left.[22 bis] A
mixture of permanganate of potassium, phosphorous
and sulphur takes fire when struck or rubbed, a
mixture of the permanganate with carbon only takes
fire when heated, not when struck. The instability of
the salt is also seen in the fact that its solution is
decomposed by peroxide of hydrogen, which at the
same time it decomposes. A number of substances
reduce potassium permanganate to manganese
dioxide (in which case the red solution becomes
colourless).[23] Many organic substances (although far
from all, even when boiled in a solution of
permanganate) act in this manner, being oxidised at
the expense of a portion of its oxygen. Thus, a
solution of sugar decomposes a cold solution of
potassium permanganate. In the presence of an
excess of alkali, with a small quantity of sugar, the
reduction leads to the formation of potassium
manganate, because 2KMnO4 + 2KHO = O +
2K2MnO4 + H2O. With a considerable amount of
sugar and a more prolonged action, the solution
turns brown and precipitates manganese dioxide or
even oxide. In the oxidation of many organic bodies
by an alkaline solution of KMnO4 generally three-
eighths of the oxygen in the salt are utilised for
oxidation: 2KMnO4 = K2O + 2MnO2 + O3. A portion
of the alkali liberated is retained by the manganese
dioxide, and the other portion generally combines
with the substance oxidised, because the latter most
frequently gives an acid with an excess of alkali. A
solution of potassium iodide acts in a similar manner,
being converted into potassium iodate at the
expense of the three atoms of oxygen disengaged by
two molecules of potassium permanganate.
In the presence of acids, potassium permanganate
acts as an oxidising agent with still greater energy
than in the presence of alkalis. At any rate, a greater
proportion of oxygen is then available for oxidation,
namely, not ⅜, as in the presence of alkalis, but ⅝,
because in the first instance manganese dioxide is
formed, and in the second case manganous oxide, or
rather the salt, MnX2, corresponding with it. Thus, for
instance, in the presence of an excess of sulphuric
acid, the decomposition is accomplished in the
following manner: 2KMnO4 + 3H2SO4 = K2SO4 +
2MnSO4 + 3H2O + 5O. This decomposition, however,
does not proceed directly on mixing a solution of the
salt with sulphuric acid, and crystals of the salt even
dissolve in oil of vitriol without the evolution of
oxygen, and this solution only decomposes by
degrees after a certain time. This is due to the fact
that sulphuric acid liberates free permanganic acid
from the permanganate,[24] which acid is stable in
solution. But if, in the presence of acids and a
permanganate, there is a substance capable of
absorbing oxygen—for instance, capable of passing
into a higher grade of oxidation—then the reduction
of the permanganic acid into manganous oxides
sometimes proceeds directly at the ordinary
temperature. This reduction is very clearly seen,
because the solutions of potassium permanganate
are red whilst the manganous salts are almost
colourless. Thus, for instance, nitrous acid and its
salts are converted into nitric acid and decolorise the
acid solution of the permanganate. Sulphurous
anhydride and its salts immediately decolorise
potassium permanganate, forming sulphuric acid.
Ferrous salts, and in general salts of lower grades of
oxidation capable of being oxidised in solution, act in
exactly the same manner. Sulphuretted hydrogen is
also oxidised to sulphuric acid; even mercury is
oxidised at the expense of permanganic acid, and
decolorises its solution, being converted into
mercuric oxide. Moreover, the end point of these
reactions may easily be seen, and therefore, having
first determined the amount of active oxygen in one
volume of a solution of potassium permanganate,
and knowing how many volumes are required to
effect a given oxidation, it is easy to determine the
amount of an oxidisable substance in a solution from
the amount of permanganate expended
(Marguerite's method).
The oxidising action of KMnO4, like all other
chemical reactions, is not accomplished
instantaneously, but only gradually. And, as the
course of the reaction is here easily followed by
determining the amount of salt unchanged in a
sample taken at a given moment,[25] the oxidising
reaction of potassium permanganate, in an acid
liquid, was employed by Harcourt and Esson (1865)
as one of the first cases for the investigation of the
laws of the rate of chemical change[26] as a subject
of great importance in chemical mechanics. In their
experiments they took oxalic acid, C2H2O_4, which in
oxidising gives carbonic anhydride, whilst, with an
excess of sulphuric acid, the potassium
permanganate is converted into manganous
sulphate, MnSO4, so that the ultimate oxidation will
be expressed by the equation: 5C2H2O4 + 2MnKO4 +
3H2SO4 = 10CO2 + K2SO4 + 2MnSO4 + 8H2O. The
influence of the relative amount of sulphuric acid is
seen from the annexed table, which gives the
measure of reaction p per 100 parts of potassium
permanganate, taken four minutes after mixing,
using n molecules of sulphuric acid, H2SO4, per
2KMnO4 + 5C2H2O4:
n = 2 4 6 8 121622
p =22365163778622
showing that in a given time (4 minutes) the
oxidation is the more perfect the greater the amount
of sulphuric acid taken for given amounts of KMnO4
and C2H2O4. It is obvious also that the temperature
and relative amount of every one of the acting and
resulting substances should show its influence on the
relative velocity of reaction; thus, for instance, direct
experiment showed the influence of the admixture of
manganous sulphate. When a large proportion of
oxalic acid (108 molecules) was taken to a large
mass of water and to 2 molecules of permanganate
14 molecules of manganous sulphate were added,
the quantity x of the potassium permanganate acted
on (in percentages of the potassium permanganate
taken) in t minutes (at 16°) was as follows:
t = 2 5 8 11 14 44 47 53 61 68
x =5·212·118·725·131·368·471·775·879·883·0
These figures show that the rate of reaction—that is,
the quantity of permanganate changed in one minute
—decreases proportionally to the decrease in the
amount of unchanged potassium permanganate. At
the commencement, about 2·6 per cent. of the salt
taken was decomposed in the course of one minute,
whilst after an hour the rate was about 0·5 per cent.
The same phenomena are observed in every case
which has been investigated, and this branch of
theoretical or physical chemistry, now studied by
many,[27] promises to explain the course of chemical
transformations from a fresh point of view, which is
closely allied to the doctrine of affinity, because the
rate of reaction, without doubt, is connected with the
magnitude of the affinities acting between the
reacting substances.

Footnotes:
[1] The working of the Ural chrome iron ore into chromium
compounds has been firmly established in Russia, thanks to the
endeavours of P. K. Ushakoff, who constructed large works for this
purpose on the river Kama, near Elabougi, where as much as 2,000
tons of ore are treated yearly, owing to which the importation of
chromium preparations into Russia has ceased.
[1 bis] But the calcium chromate is soluble in water in the
presence of an excess of chromic acid, as may be seen from the fact
that a solution of chromic acid dissolves lime.
[2] There are many variations in the details of the manufacturing
processes, and these must be looked for in works on technical
chemistry. But we may add that the chromate may also be obtained
by slightly roasting briquettes of a mixture of chrome iron and lime,
and then leaving the resultant mass to the action of moist air
(oxygen is absorbed, and the mass turns yellow).
[2 bis] The oxidising action of potassium dichromate on organic
substances at the ordinary temperature is especially marked under
the action of light. Thus it acts on gelatin, as Poutven discovered;
this is applied to photography in the processes of photogravure,
photo-lithography, pigment printing, &c. Under the action of light
this gelatin is oxidised, and the chromic anhydride deoxidised into
chromic oxide, which unites with the gelatin and forms a compound
insoluble in warm water, whilst where the light has not acted, the
gelatin remains soluble, its properties being unaffected by the
presence of chromic acid or potassium dichromate.
[3] Ammonium and sodium dichromates are now also prepared on
a large scale. The sodium salts may be prepared in exactly the same
manner as those of potassium. The normal salt combines with ten
equivalents of water, like Glauber's salt, with which it is
isomorphous. Its solution above 30° deposits the anhydrous salt.
Sodium dichromate crystals contain Na2Cr2O7,2H2O. The ammonium
salts of chromic acid are obtained by saturating the anhydride itself
with ammonia. The dichromate is obtained by saturating one part of
the anhydride with ammonia, and then adding a second part of
anhydride and evaporating under the receiver of an air-pump. On
ignition, the normal and acid salts leave chromic oxide. Potassium
ammonium chromate, NH4KCrO4, is obtained in yellow needles from
a solution of potassium dichromate in aqueous ammonia; it not only
loses ammonia and becomes converted into potassium dichromate
when ignited, but also by degrees at the ordinary temperature. This
shows the feeble energy of chromic acid, and its tendency to form
stable dichromates. Magnesium chromate is soluble in water, as also
is the strontium salt. The calcium salt is also somewhat soluble, but
the barium salt is almost insoluble. The isomorphism with sulphuric
acid is shown in the chromates by the fact that the magnesium and
ammonium salts form double salts containing six equivalents of
water, which are perfectly isomorphous with the corresponding
sulphates. The magnesium salt crystallises in large crystals
containing seven equivalents of water. The beryllium, cerium, and
cobalt salts are insoluble in water. Chromic acid dissolves
manganous carbonate, but on evaporation the solution deposits
manganese dioxide, formed at the expense of the oxygen of the
chromic acid. Chromic acid also oxidises ferrous oxide, and ferric
oxide is soluble in chromic acid.
One of the chromates most used by the dyer is the insoluble
yellow lead chromate, PbCrO4 (Chapter XVIII., Note 46), which is
precipitated on mixing solutions of PbX2 with soluble chromates. It
easily forms a basic salt, having the composition PbO,PbCrO4, as a
crystalline powder, obtained by fusing the normal salt with nitre and
then rapidly washing in water. The same substance is obtained,
although impure and in small quantity, by treating lead chromate
with neutral potassium chromate, especially on boiling the mixture;
and this gives the possibility of attaining, by means of these
materials, various tints of lead chromate, from yellow to red, passing
through different orange shades. The decomposition which takes
place (incompletely) in this case is as follows: 2PbCrO4 + K2CrO4 =
PbCrO4,PbO + K2Cr2O7—that is, potassium dichromate is formed in
solution.
[4] The sulphuric acid should not contain any lower oxides of
nitrogen, because they reduce chromic anhydride into chromic