Etymology
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chief (adj.)

c. 1300, "highest in rank or power; most important or prominent; supreme, best, placed above the rest," from Old French chief "chief, principal, first" (10c., Modern French chef), from Vulgar Latin *capum (also source of Spanish and Portuguese cabo, Italian capo, Provençal cap), from Latin caput "head," also "leader, guide, chief person; summit; capital city" (from PIE root *kaput- "head").

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chief (n.)

c. 1300, "head, leader, captain; the principal or most important part of anything;" from Old French chief "leader, ruler, head" of something, "capital city" (10c., Modern French chef), from Vulgar Latin *capum, from Latin caput "head," also "leader, chief person; summit; capital city" (from PIE root *kaput- "head"). Meaning "head of a clan" is from 1570s; later extended to headmen of Native American tribes (by 1713; William Penn, 1680s, called them kings). Commander-in-chief is attested from 1660s.

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chiefdom (n.)

1570s, "sovereignty," from chief (n.) + -dom.

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chiefly (adv.)

"pre-eminently, above all, in the first place," mid-14c., from chief (adj.) + -ly (2). Adjectival meaning "pertaining to a chief" is from 1870 (from chief + -ly (1)).

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chef (n.)

"head cook," 1842, from French chef, short for chef de cuisine, literally "head of the kitchen," from Old French chief "leader, ruler, head" (see chief (n.)).

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*kaput- 
Proto-Indo-European root meaning "head."

It forms all or part of: achieve; behead; biceps; cabbage; cabochon; caddie; cadet; cap; cap-a-pie; cape (n.1) "garment;" cape (n.2) "promontory;" capital (adj.); capital (n.3) "head of a column or pillar;" capitate; capitation; capitulate; capitulation; capitulum; capo (n.1) "leader of a Mafia family;" capo (n.2) "pitch-altering device for a stringed instrument;" caprice; capsize; captain; cattle; caudillo; chapter; chef; chief; chieftain; corporal (n.); decapitate; decapitation; forehead; head; hetman; kaput; kerchief; mischief; occipital; precipice; precipitate; precipitation; recapitulate; recapitulation; sinciput; triceps.

It is the hypothetical source of/evidence for its existence is provided by: Sanskrit kaput-; Latin caput "head;" Old English heafod, German Haupt, Gothic haubiþ "head."
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ch 

digraph used in Old French for the "tsh" sound. In some French dialects, including that of Paris (but not that of Picardy), Latin ca- became French "tsha." This was introduced to English after the Norman Conquest, in words borrowed from Old French such as chaste, charity, chief (adj.). Under French influence, -ch- also was inserted into Anglo-Saxon words that had the same sound (such as bleach, chest, church) which in Old English still was written with a simple -c-, and into those that had formerly been spelled with a -c- and pronounced "k" such as chin and much.

As French evolved, the "t" sound dropped out of -ch-, so in later loan-words from French -ch- has only the sound "sh-" (chauffeur, machine (n.), chivalry, etc.).

It turns up as well in words from classical languages (chaos, echo, etc.). Most uses of -ch- in Roman Latin were in words from Greek, which in Greek would be pronounced correctly as /k/ + /h/, as in modern blockhead, but most Romans would have said merely /k/, and this was the regular pronunciation in English. Before c. 1500 such words were regularly spelled with a -c- (Crist, cronicle, scoole), but Modern English has preserved or restored the etymological spelling in most of them (chemical, chorus, monarch). 

Sometimes ch- is written to keep -c- hard before a front vowel, as still in modern Italian. In some languages (Welsh, Spanish, Czech) ch- can be treated as a separate letter and words in it are alphabetized after -c- (or, in Czech and Slovak, after -h-). The sound also is heard in words from more distant languages (as in cheetah, chintz), and the digraph also is used to represent the sound in Scottish loch.

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chieftain (n.)

early 14c., cheftayne "ruler, chief, head" of something, from Anglo-French chiefteyn, Old French chevetain "captain, chief, leader," from Late Latin capitaneus "commander," from Latin capitis, genitive of caput "head" (from PIE root *kaput- "head"). Now mostly poetic or archaic; in "Rob Roy" (1818) a Highland chieftain was the head of a branch of a clan, a chief was the head of the whole name. Related: Chieftainship; chieftaincy.

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ras 

Ethiopian title of chief ministers, generals, governors, etc., from Amharic ras "chief, head," from Arabic ra's.

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arch- 
also archi-, word-forming element meaning "chief, principal; extreme, ultra; early, primitive," from Latinized form of Greek arkh-, arkhi- "first, chief, primeval," combining form of arkhos "a chief, leader, commander," arkhein "be first, begin" (see archon).
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