Does any living language contrast /kʷ/ and /kw/?
If yes, is there a way I can hear a minimal pair spoken?
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In theory, yes. Tashlhiyt Berber is said to have a contrast, but that does not mean that there are any minimal pairs. That article points to literature, saying that it is generally agreed that they are different. However, the article slightly undermines the claim by noting that [kw] and [kʷ] differ in terms of syllabification: which (potentially) means that the distinction is not [kʷ] vs. [kw], it resides in distinctive syllabification. That means that it depends on what you mean by "minimal pair". Tigrinya has a similar potential, that k+w sequences can be constructed and there is a /kʷ/ phoneme, but the actual phonetic values have other low-level properties associated with the sequence vs. single segment. In both cases, there's a good argument that kw is different, phonologically, from kʷ, but I suspect that minimal pairs are a deal-breaker.
Thai can be what you are looking for.
It has onset clusters
/kʰw/. Quite often, they are realized as labialized velar consonants
However¹, final stops like
/-k/ are accompanied by a simultaneous glottal stop, thus making syllable boundaries well defined by intersyllabic juncture. This prevents any C-to-C coarticulation and resyllabification of final consonants.
So if there are two adjacent syllables, one ends with the final
/-k/ and another starts with
/w-/, they remain audibly separate.
Compare (press 🔈 speaker icon to listen):
[tʰúk wan]"every day"
Just because a language contrasts two sounds, doesn't mean there should be minimal pairs (cf. English /h/ and /ŋ/).
The IPA uses a plain w to symbolise the [w] sound (war) and a superscript ʷ for labialisation (i.e. secondary articulation). There's a constriction at the velum for w, but ʷ doesn't have any constriction at the velum, it's simply the roundedness of the lips.
Now the sequence [kw] consists of two sounds having two points of articulation (primary articulation) the constriction is made at the velum for both the sounds (velar throughout) whereas [kʷ] only has one point of primary articulation at the velum (the ʷ means that the lips are rounded at the same time of articulation of the [k]). The best way to understand this is to think of the English words queen and cool (ignoring [-iːn] [-uːl]): in the former case, there are two sounds having two primary articulations (i.e. [w] after [k]). The latter, however, has only one primary articulation (that of [k]) but if you look closely at your lips, you'll see that they're rounded in anticipation of the following rounded vowel ([u]).
Labialisation isn't phonemic in English, but phonetically, compare the following words:
For many speakers of English, the [s] in soon and soup is labialised due to anticipation of the following rounded vowel. It means English contrasts [sʷ] and [sw] only phonetically.
There are a few minimal pairs distinguishing [kʷ] and [kw] (not /kʷ/ and /kw/) in (British) English:
Some of these qu- words are quite rare and I've never heard then before but they do exist.
Some Salishan and Wakashan languages are said to contrast /kw/ and /kʷ/, but I haven't been able to find minimal pairs.
The Wakashan language Makah has a phonemic contrast between /k/ and /kʷ/. Waka'wala contrasts /kʲ/ and /kʷ/. Nahuatl also has a phonemic contrast between /kʷ/ and /k/ and I assume it also contrasts /kʷ/ and /kw/.